U.S. patent application number 10/133808 was filed with the patent office on 2003-05-29 for hydrophilic polymers and methods of preparation.
This patent application is currently assigned to Avery Dennison Corporation. Invention is credited to Holguin, Daniel L..
Application Number | 20030100694 10/133808 |
Document ID | / |
Family ID | 29268784 |
Filed Date | 2003-05-29 |
United States Patent
Application |
20030100694 |
Kind Code |
A1 |
Holguin, Daniel L. |
May 29, 2003 |
Hydrophilic polymers and methods of preparation
Abstract
The present invention provides a method for the preparation of
hydrophilic water insoluble, gel-free copolymers of 2-hydroxyethyl
methacrylate and at least one of acrylic acid or methacrylic acid,
and 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate and
acrylic or methacrylic acid, where the copolymers are prepared in a
solution of water and alcohol using monomeric 2-hydroxyethyl
methacrylate containing ethylene glycol dimethacrylate impurities
up to about 0.15% by weight and substantially in the absence of a
chain transfer agent. The copolymers are convertible to water
soluble copolymers by pH adjustment. The invention also provides a
method for the preparation of a copolymer of 2-hydroxyethyl
methacrylate and 4-hydroxybutyl acrylate, and a homopolymer of
2-hydroxyethyl methacrylate in a solution of water and either a
monoalcohol or a polyhydric alcohol. The polymers are useful in
topical skin applications, including use as cosmetic compositions,
dermatological compositions, and flexible skin coatings, and as
pressure sensitive adhesives.
Inventors: |
Holguin, Daniel L.;
(Fullerton, CA) |
Correspondence
Address: |
JOSEPH G CURATOLO, ESQ.
RENNER KENNER GREIVE BOBAK TAYLOR & WEBER
24500 CENTER RIDGE ROAD, SUITE 280
WESTLAKE
OH
44145
US
|
Assignee: |
Avery Dennison Corporation
Pasadena
CA
91103
|
Family ID: |
29268784 |
Appl. No.: |
10/133808 |
Filed: |
April 26, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10133808 |
Apr 26, 2002 |
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09757980 |
Jan 10, 2001 |
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09757980 |
Jan 10, 2001 |
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09540252 |
Mar 31, 2000 |
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Current U.S.
Class: |
526/317.1 ;
428/50; 526/210; 526/212; 526/217; 526/318.3; 526/318.4;
526/318.42; 526/320; 526/329.2; 526/74; 526/89 |
Current CPC
Class: |
A61Q 19/00 20130101;
A61K 9/7023 20130101; B41M 5/5245 20130101; Y10T 428/167 20150115;
B41M 5/5236 20130101; A61Q 17/00 20130101; A61K 8/042 20130101;
B41M 5/5227 20130101; B41M 5/5254 20130101; C08F 220/281 20200201;
B41M 5/508 20130101; Y02P 20/582 20151101; A61K 8/8152 20130101;
C08F 220/20 20130101; B41M 5/52 20130101; C08F 220/281 20200201;
C08F 220/281 20200201; C08F 220/281 20200201; C08F 220/281
20200201; C08F 222/102 20200201; C08F 220/281 20200201; C08F
220/281 20200201; C08F 222/102 20200201 |
Class at
Publication: |
526/317.1 ;
526/74; 526/89; 526/210; 526/212; 526/217; 526/318.3; 526/318.4;
526/318.42; 526/329.2; 526/320; 428/50 |
International
Class: |
C08F 120/06 |
Claims
I claim:
1. A method for the preparation of a gel-free, water-insoluble,
hydrophilic copolymer of 2-hydroxyethyl methacrylate and acrylic
acid or methacrylic acid substantially in the absence of a chain
transfer agent comprising: introducing monomeric 2-hydroxyethyl
methacrylate containing ethylene glycol dimethacrylate impurities
up to about 0.15% by weight, based on the weight of the monomer,
and at least one of acrylic acid or methacrylic acid into a
solution of water and alcohol; and copolymerizing the
2-hydroxyethyl methacrylate and the at least one of acrylic acid or
methacrylic acid to form a polymerization mixture.
2. The method of claim 1, wherein the monomeric 2-hydroxyethyl
methacrylate contains ethylene glycol dimethacrylate impurities in
the range of about 0.05% to about 0.1% by weight, based on the
weight of the monomer.
3. The method of claim 1, wherein the monomeric 2-hydroxyethyl
methacrylate contains impurities in a total amount of no more than
about 3% by weight, based on the weight of the monomer, and wherein
the impurities are selected from the group consisting of ethylene
glycol dimethacrylate, diethylene glycol monomethacrylate,
methacrylic acid and mixtures thereof.
4. The method of claim 1, further comprising leaching the copolymer
of 2-hydroxyethyl methacrylate and at least one of acrylic acid or
methacrylic acid to substantially remove residual monomer.
5. The method of claim 4, wherein the polymerization mixture is
leached and precipitated with water to substantially remove
residual monomer.
6. The method of claim 5, wherein the copolymer precipitate is
redissolved in a liquid selected from the group consisting of
alcohols, alkylene glycols and polyalkylene glycols.
7. The method of claim 5, further comprising adjusting the pH of
the polymerization mixture to a pH sufficient to render the
copolymer water soluble.
8. The method of claim 7, comprising adjusting the pH of the
polymerization mixture to a pH of greater than about 4.5.
9. The method of claim 8, wherein the pH of the polymerization
mixture is adjusted to a pH of about 5.5 to about 7.5.
10. A water insoluble copolymer prepared in accordance with claim
1.
11. A water soluble copolymer prepared in accordance with claim
7.
12. The method of claim 1, further comprising adding a polyalkylene
glycol to the polymerization mixture and substantially removing the
solution of alcohol and water, to form a hydrophilic pressure
sensitive adhesive.
13. The method of claim 12, wherein the polyalkylene glycol is
selected from the group consisting of polyethylene glycol,
polypropylene glycol, copolymers of ethylene glycol and propylene
glycol, and mixtures thereof.
14. The method of claim 13, wherein the polyalkylene glycol is
polyethylene glycol.
15. The method of claim 4, further comprising adding a polyalkylene
glycol to the polymerization mixture and substantially removing the
solution of alcohol and water, to form a hydrophilic pressure
sensitive adhesive.
16. The method of claim 15, wherein the polyalkylene glycol is
selected from the group consisting of polyethylene glycol,
polypropylene glycol, copolymers of ethylene glycol and propylene
glycol, and mixtures thereof.
17. The method of claim 16, wherein the polyalkylene glycol is
polyethylene glycol.
18. The method of claim 7, further comprising adding a polyalkylene
glycol to the polymerization mixture and substantially removing the
solution of alcohol and water, to form a hydrophilic pressure
sensitive adhesive.
19. The method of claim 18, wherein the polyalkylene glycol is
selected from the group consisting of polyethylene glycol,
polypropylene glycol, copolymers of ethylene glycol and propylene
glycol, and mixtures thereof.
20. The method of claim 19, wherein the polyalkylene glycol is
polyethylene glycol.
21. A pressure sensitive adhesive prepared in accordance with claim
12.
22. A pressure sensitive adhesive prepared in accordance with claim
15.
23. A pressure sensitive adhesive prepared in accordance with claim
18.
24. The method of claim 1, further comprising adding a flexiblizing
agent to the polymerization mixture and substantially removing the
solution of alcohol and water, to form a flexible coating.
25. The method of claim 24, wherein the flexiblizing agent is
selected from glycerin and propylene glycol.
26. A flexible coating prepared in accordance with the method of
claim 24.
27. The method of claim 4, further comprising adding a flexiblizing
agent to the polymerization mixture and substantially removing the
solution of alcohol and water, to form a flexible coating.
28. The method of claim 27, wherein the flexiblizing agent is
selected from glycerin and propylene glycol.
29. A flexible coating prepared in accordance with the method of
claim 27.
30. The method of claim 7, further comprising adding a flexiblizing
agent to the polymerization mixture and substantially removing the
solution of alcohol and water, to form a flexible coating.
31. The method of claim 30, wherein the flexiblizing agent is
selected from glycerin and propylene glycol.
32. A flexible coating prepared in accordance with the method of
claim 30.
33. A cosmetic composition containing the copolymer prepared in
accordance with claim 1.
34. A topical skin composition selected from the group consisting
of a cream, lotion, ointment, gel, aerosol, and spray; each
comprising the copolymer prepared by the method of claim 1.
35. A cosmetic composition containing the copolymer prepared in
accordance with claim 4.
36. A topical skin composition selected from the group consisting
of a cream, lotion, ointment, gel, aerosol, and spray; each
comprising the copolymer prepared by the method of claim 4.
37. A cosmetic composition containing the copolymer prepared in
accordance with claim 7.
38. A topical skin composition selected from the group consisting
of a cream, lotion, ointment, gel, aerosol, and spray; each
comprising the copolymer prepared by the method of claim 7.
39. A method for the preparation of a gel-free, water insoluble,
hydrophilic copolymer of 2-hydroxyethyl methacrylate,
4-hydroxybutyl acrylate and at least one of acrylic acid or
methacrylic acid substantially in the absence of a chain transfer
agent comprising: introducing monomeric 2-hydroxyethyl
methacrylate, 4-hydroxybutyl acrylate and at least one of acrylic
acid or methacrylic acid into a solution of water and alcohol,
wherein the monomeric 2-hydroxyethyl methacrylate contains ethylene
glycol dimethacrylate impurities up to about 0.15% by weight, based
on the weight of the monomer; and copolymerizing the monomeric
2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate and at least
one of acrylic acid or methacrylic acid to form a polymerization
mixture.
40. The method of claim 39, wherein the monomeric 2-hydroxyethyl
methacrylate contains ethylene glycol dimethacrylate impurities in
the range of about 0.05% to about 0.1% by weight, based on the
weight of the monomer.
41. The method of claim 39, wherein the monomeric 2-hydroxyethyl
methacrylate contains impurities in a total amount of no more than
about 3% by weight, based on the weight of the monomer, and wherein
the impurities are selected from the group consisting of ethylene
glycol dimethacrylate, diethylene glycol monomethacrylate,
methacrylic acid and mixtures thereof.
42. The method of claim 39, further comprising leaching the
copolymer of 2-hydroxyethyl methacrylate, 4-hydroxybutyl
methacrylate and at least one of acrylic acid or methacrylic acid
to substantially remove residual monomer.
43. The method of claim 42, wherein the polymerization mixture is
leached and precipitated with water to substantially remove
residual monomer.
44. The method of claim 43, wherein the copolymer precipitate is
redissolved in a liquid selected from the group consisting of
alcohols, alkylene glycols and polyalkylene glycols.
45. The method of claim 42, further comprising adjusting the pH of
the polymerization mixture to a pH sufficient to render the
copolymer water soluble.
46. The method of claim 45, comprising adjusting the pH of the
polymerization mixture to a pH of greater than about 4.5.
47. The method of claim 46, wherein the pH of the polymerization
mixture is adjusted to a pH of about 5.5 to about 7.5.
48. A water insoluble copolymer prepared in accordance with claim
39.
49. A water soluble copolymer prepared in accordance with claim
45.
50. The method of claim 39, further comprising adding a
polyalkylene glycol to the polymerization mixture and substantially
removing the solution of alcohol and water, to form a hydrophilic
pressure sensitive adhesive.
51. The method of claim 50, wherein the polyalkylene glycol is
selected from the group consisting of polyethylene glycol,
polypropylene glycol, copolymers of ethylene glycol and propylene
glycol, and mixtures thereof.
52. The method of claim 51, wherein the polyalkylene glycol is
polyethylene glycol.
53. A pressure sensitive adhesive prepared in accordance with claim
50.
54. The method of claim 42, further comprising adding a
polyalkylene glycol to the polymerization mixture and substantially
removing the solution of alcohol and water, to form a hydrophilic
pressure sensitive adhesive.
55. The method of claim 54, wherein the polyalkylene glycol is
selected from the group consisting of polyethylene glycol,
polypropylene glycol, copolymers of ethylene glycol and propylene
glycol, and mixtures thereof.
56. The method of claim 55, wherein the polyalkylene glycol is
polyethylene glycol.
57. A pressure sensitive adhesive prepared in accordance with claim
54.
58. The method of claim 45, further comprising adding a
polyalkylene glycol to the polymerization mixture and substantially
removing the solution of alcohol and water, to form a hydrophilic
pressure sensitive adhesive.
59. The method of claim 58, wherein the polyalkylene glycol is
selected from the group consisting of polyethylene glycol,
polypropylene glycol, copolymers of ethylene glycol and propylene
glycol, and mixtures thereof.
60. The method of claim 59, wherein the polyalkylene glycol is
polyethylene glycol.
61. A pressure sensitive adhesive prepared in accordance with claim
58.
62. The method of claim 39, further comprising adding a
flexiblizing agent to the polymerization mixture and substantially
removing the solution of alcohol and water, to form a flexible
coating.
63. The method of claim 62, wherein the flexiblizing agent is
selected from glycerin and propylene glycol.
64. A flexible coating prepared in accordance with the method of
claim 62.
65. The method of claim 42, further comprising adding a
flexiblizing agent to the polymerization mixture and substantially
removing the solution of alcohol and water, to form a flexible
coating.
66. The method of claim 65, wherein the flexiblizing agent is
selected from glycerin and propylene glycol.
67. A flexible coating prepared in accordance with the method of
claim 65.
68. The method of claim 45, further comprising adding a
flexiblizing agent to the polymerization mixture and substantially
removing the solution of alcohol and water, to form a flexible
coating.
69. The method of claim 68, wherein the flexiblizing agent is
selected from glycerin and propylene glycol.
70. A flexible coating prepared in accordance with the method of
claim 68.
71. A cosmetic composition containing the copolymer prepared in
accordance with claim 39.
72. A topical skin composition selected from the group consisting
of a cream, lotion, ointment, gel, aerosol, and spray, each
comprising the copolymer of claim 39.
73. A cosmetic composition containing the copolymer prepared in
accordance with claim 42.
74. A topical skin composition selected from the group consisting
of a cream, lotion, ointment, gel, aerosol, and spray; each
comprising the copolymer prepared by the method of claim 42.
75. A cosmetic composition containing the copolymer prepared in
accordance with claim 45.
76. A topical skin composition selected from the group consisting
of a cream, lotion, ointment, gel, aerosol, and spray; each
comprising the copolymer prepared by the method of claim 45.
77. A method for the preparation of a substantially
monoalcohol-free, gel-free, water insoluble, hydrophilic copolymer
of 2-hydroxyethyl methacrylate and 4-hydroxybutyl acrylate
substantially in the absence of a chain transfer agent comprising:
introducing monomeric 2-hydroxyethyl methacrylate containing
ethylene glycol dimethacrylate impurities up to about 0.15% by
weight, based on the weight of the monomer, and monomeric
4-hydroxybutyl acrylate into a solution of water and a mono
alcohol; copolymerizing the monomeric 2-hydroxyethyl methacrylate
and the 4-hydroxybutyl acrylate to form a polymerization mixture;
leaching the copolymer of 2-hydroxyethyl methacrylate and
4-hydroxybutyl acrylate to substantially remove residual monomer;
and substantially replacing the monoalcohol with a polyhydric
alcohol.
78. The method of claim 77, wherein the copolymer, after leaching
and replacing, contains less than about 1 weight percent of the
monoalcohol.
79. The method of claim 78, wherein the copolymer, after leaching
and replacing, contains less than about 0.5 weight percent of the
monoalcohol.
80. The method of claim 77, wherein the polyhydric alcohol is
selected from the group consisting of alkylene glycols, alkyl
ethers of alkylene glycols, diols, glycerin and alkyl esters of
glycerin.
81. The method of claim 77, wherein the alkylene glycol is selected
from the group consisting of ethylene glycol and propylene
glycol.
82. The method of claim 81, wherein the alkylene glycol is
propylene glycol.
83. The method of claim 80, wherein the alkyl ethers of an alkylene
glycol are selected from the group consisting of ethylene glycol
monomethyl ether, ethylene glycol monoethyl ether, propylene glycol
monomethyl ether and propylene glycol monoethyl ether.
84. The method of claim 80, wherein the diols are selected from the
group consisting of 1,3-butanediol, 1,4-butanediol,
2-methyl-2,4-pentanediol, 2,5 hexanediol and 2,4-heptanediol.
85. The method of claim 80, wherein the polyhydric alcohol is
glycerin.
86. The method of claim 80, wherein the alkyl esters of glycerin
are selected from the group consisting of glycerin monolaurate,
glycerin monooleate and glycerin monostearate.
87. The method of claim 77, wherein the monomeric 2-hydroxyethyl
methacrylate contains ethylene glycol dimethacrylate impurities in
the range of about 0.05% to about 0.1% by weight, based on the
weight of the monomer.
88. The method of claim 77, wherein the monomeric 2-hydroxyethyl
methacrylate contains impurities in a total amount of no more than
about 3% by weight, based on the weight of the monomer, and wherein
the impurities are selected from the group consisting of ethylene
glycol dimethacrylate, diethylene glycol monomethacrylate,
methacrylic acid and mixtures thereof.
89. The method of claim 77, wherein the polymerization mixture is
leached and precipitated with water to remove residual monomer.
90. A substantially monoalcohol-free, gel-free, water insoluble,
hydrophilic copolymer prepared in accordance with claim 77.
91. The method of claim 77, further comprising substantially
removing the water from the leached and replaced copolymer to form
a flexible coating.
92. A flexible coating prepared in accordance with the method of
claim 91.
93. A cosmetic composition containing the copolymer prepared in
accordance with claim 77.
94. A topical skin composition selected from the group consisting
of a cream, lotion, ointment, gel, aerosol, and spray; each
comprising the copolymer prepared by the method of claim 77.
95. A method for the preparation of a substantially
monoalcohol-free, gel-free, water insoluble, hydrophilic copolymer
of 2-hydroxyethyl methacrylate and 4-hydroxybutyl acrylate
substantially in the absence of a chain transfer agent comprising:
introducing monomeric 2-hydroxyethyl methacrylate containing
ethylene glycol dimethacrylate impurities up to about 0.15% by
weight, based on the weight of the monomer, and monomeric
4-hydroxybutyl acrylate into a solution of water and polyhydric
alcohol; copolymerizing the monomeric 2-hydroxyethyl methacrylate
and the 4-hydroxybutyl acrylate to form a polymerization
mixture.
96. The method of claim 95, further comprising leaching the
copolymer of 2-hydroxyethyl methacrylate and 4-hydroxybutyl
acrylate to substantially remove residual monomer.
97. The method of claim 96, further comprising substantially
replacing the polyhydric alcohol with a monoalcohol.
98. The method of claim 97, wherein the monoalcohol is selected
from ethanol and methanol.
99. The method of claim 95, wherein the monomeric 2-hydroxyethyl
methacrylate contains ethylene glycol dimethacrylate impurities in
the range of about 0.05% to about 0.1% by weight, based on the
weight of the monomer.
100. The method of claim 95, wherein the monomeric 2-hydroxyethyl
methacrylate contains impurities in a total amount of no more than
about 3% by weight, based on the weight of the monomer, and wherein
the impurities are selected from the group consisting of ethylene
glycol dimethacrylate, diethylene glycol monomethacrylate,
methacrylic acid and mixtures thereof.
101. A cosmetic composition containing the copolymer prepared in
accordance with claim 95.
102. A topical skin composition selected from the group consisting
of a cream, lotion, ointment, gel, aerosol, and spray; each
comprising the copolymer prepared by the method of claim 95.
103. A method for the preparation of a substantially
monoalcohol-free, gel-free, water insoluble, hydrophilic
homopolymer of 2-hydroxyethyl methacrylate substantially in the
absence of a chain transfer agent comprising: introducing monomeric
2-hydroxyethyl methacrylate containing ethylene glycol
dimethacrylate impurities up to about 0.15% by weight, based on the
weight of the monomer, into a solution of water and a monoalcohol;
polymerizing the 2-hydroxyethyl methacrylate to form a
polymerization mixture; leaching the homopolymer of 2-hydroxyethyl
methacrylate to substantially remove residual monomer; and
substantially replacing the monoalcohol with a polyhydric
alcohol.
104. The method of claim 103, wherein the homopolymer, after
leaching and replacing, contains less than about 1 weight percent
of the monoalcohol.
105. The method of claim 103, wherein the homopolymer, after
leaching and replacing, contains less than about 0.5 weight percent
of the monoalcohol.
106. The method of claim 103, wherein the polyhydric alcohol is
selected from the group consisting of alkylene glycols, alkyl
ethers of an alkylene glycol, diols, glycerin and alkyl esters of
glycerin.
107. The method of claim 106, wherein the alkylene glycol is
selected from the group consisting of ethylene glycol and propylene
glycol.
108. The method of claim 107, wherein the alkylene glycol is
propylene glycol.
109. The method of claim 106, wherein the alkyl ethers of an
alkylene glycol are selected from the group consisting of ethylene
glycol monomethyl ether, ethylene glycol monoethyl ether, propylene
glycol monomethyl ether and propylene glycol monoethyl ether.
110. The method of claim 106, wherein the diol is selected from the
1,3-butanediol, 1,4-butanediol, 2-methyl-2,4-pentanediol,
2,5-hexanediol and 2,4-heptanediol.
111. The method of claim 106, wherein the polyhydric alcohol is
glycerin.
112. The method of claim 106, wherein the alkyl esters of glycerin
can be selected form the group consisting of glycerin monolaurate,
glycerin monooleate and glycerin monostearate.
113. The method of claim 103, wherein the monomeric 2-hydroxyethyl
methacrylate contains ethylene glycol dimethacrylate impurities in
the range of about 0.05% to about 0.1% by weight, based on the
weight of the monomer.
114. The method of claim 104, wherein the monomeric 2-hydroxyethyl
methacrylate contains impurities in a total amount of no more than
about 3% by weight, based on the weight of the monomer, and wherein
the impurities are selected from the group consisting of ethylene
glycol dimethacrylate, diethylene glycol monomethacrylate,
methacrylic acid and mixtures thereof.
115. The method of claim 103, wherein the polymerization mixture is
leached and precipitated with water to substantially remove
residual monomer.
116. A substantially monoalcohol-free, gel-free, water insoluble,
hydrophilic polymer prepared in accordance with claim 103.
117. The method of claim 115, further comprising substantially
removing the water from the homopolymer, after leaching and
replacing, to form a flexible coating.
118. A flexible coating prepared in accordance with the method of
claim 117.
119. A cosmetic composition containing the homopolymer prepared in
accordance with claim 103.
120. A topical skin composition selected from the group consisting
of a cream, lotion, ointment, gel, aerosol, and spray; each
containing the homopolymer prepared by the method of claim 103.
121. A method for the preparation of a substantially gel-free,
water insoluble, hydrophilic homopolymer of 2-hydroxyethyl
methacrylate substantially in the absence of a chain transfer agent
comprising: introducing monomeric 2-hydroxyethyl methacrylate
containing ethylene glycol dimethacrylate impurities up to about
0.15% by weight, based on the weight of the monomer, into a
solution of water and polyhydric alcohol; and polymerizing the
2-hydroxyethyl methacrylate to form a polymerization mixture.
122. The method of claim 121, further comprising leaching the
homopolymer of 2-hydroxyethyl methacrylate to substantially remove
residual monomer.
123. The method of claim 121, further comprising substantially
replacing the polyhydric alcohol with a monoalcohol.
124. The method of claim 121, wherein the monomeric 2-hydroxyethyl
methacrylate contains ethylene glycol dimethacrylate impurities in
the range of about 0.05% to about 0.1% by weight, based on the
weight of the monomer.
125. The method of claim 121, wherein the monomeric 2-hydroxyethyl
methacrylate contains impurities in a total amount of no more than
about 3% by weight, based on the weight of the monomer, and wherein
the impurities are selected from the group consisting of ethylene
glycol dimethacrylate, diethylene glycol monomethacrylate,
methacrylic acid and mixtures thereof.
126. A substantially mono alcohol-free, gel-free, water insoluble,
hydrophilic polymer prepared in accordance with claim 121.
127. The method of claim 121, further comprising substantially
removing the water from the homopolymer, after leaching and
replacing, to form a flexible coating.
128. A flexible coating prepared in accordance with the method of
claim 127.
129. A cosmetic composition containing the homopolymer prepared in
accordance with claim 121.
130. A topical skin composition selected from the group consisting
of a cream, lotion, ointment, gel, aerosol, and spray; each
containing the homopolymer prepared by the method of claim 121.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation-in-part of U.S.
Ser. No. 09/757,980, filed on Jan. 10, 2001, which is a
continuation-in-part of U.S. Ser. No. 09/540,252, filed on Mar. 31,
2000, both of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] The family of synthetic hydrophilic polymers includes
polyacrylic acid, polyvinyl pyrrolidone, polyvinyl alcohol,
polyacrylamide, poly hydroxybutyl acrylate, and poly 2-hydroxyethyl
methacrylate. In this family of synthetic hydrophilic polymers,
poly 2-hydroxyethyl methacrylate and poly hydroxybutyl acrylate are
water insoluble polymers prepared from a water soluble monomer. The
other polymers require crosslinking to form a water insoluble
polymer.
[0003] 2-Hydroxyethyl methacrylate polymers are of interest because
of their biocompatibility, as evidenced by excellent performance in
animal implant studies. The extensive use of 2-hydroxyethyl
methacrylate polymers for contact lenses for the eyes illustrates
the non irritating nature of the polymers.
[0004] Other than commercial use in contact lenses, 2-hydroxyethyl
methacrylate polymers have had limited commercial success, used at
low percentages only, because of the nature of the monomer.
Industrial grade 2-hydroxyethyl methacrylate monomer contains a
small amount of crosslinker impurity, which can cause gel formation
during solvent polymerization. The preparation of 2-hydroxyethyl
methacrylate polymer, therefore, generally requires the use of very
pure and expensive monomer having ethylene glycol dimethacrylate
impurities less than 0.035 weight percent, based on the weight of
the monomer, or a very extensive and expensive polymerization
process.
[0005] U.S. Pat. No. 2,976,576 describes the use of poly
2-hydroxyethyl methacrylate resin for contact lenses and body
implants.
[0006] U.S. Pat. No. 3,220,960 describes the use of poly
2-hydroxyethyl methacrylate resin for contact lenses and body
implants.
[0007] U.S. Pat. No. 3,567,760 describes the preparation of
2-hydroxyethyl methacrylate copolymers in methanol that are water
soluble salts for entrapping drugs, pesticides, flavoring agents,
and fragrances.
[0008] U.S. Pat. No. 3,963,685 describes the preparation of
methanol soluble poly 2-hydroxyethyl methacrylate for wound care
dressings using high purity 2-hydroxyethyl methacrylate monomer
having not over 0.035 weight percent of alkylene glycol
dimethacrylate impurities.
[0009] EP 024164A1 describes the preparation of methanol soluble
poly 2-hydroxyethyl methacrylate using high purity 2-hydroxyethyl
methacrylate monomer.
[0010] Polymer International, vol. 36 no. 4, pp.303-308 (April
1995), describes the preparation of dimethylformamide soluble poly
2-hydroxyethyl methacrylate using a chain transfer agent to prevent
gellation.
[0011] U.S. Pat. No. 4,303,066 describes the use of a plasticized
poly 2-hydroxyethyl methacrylate resin prepared from high purity
monomer as a non-tacky synthetic film for skin burns, with
shortened forming time by adding water to the mixture.
[0012] U.S. Pat. No. 4,593,053 describes the use of a plasticized
polyvinyl pyrrolidone as a hydrophilic medical type pressure
sensitive adhesive for biomedical electrodes and transdermal
devices.
[0013] WO 92/11825 describes the use of plasticized poly
2-hydroxyethyl methacrylate resin as a hydrophilic medical type
pressure sensitive adhesive for a medical device.
[0014] U.S. Pat. No. 5,225,473 describes the use of a UV cured
plasticized polyvinyl pyrrolidone as a hydrophilic medical type
pressure sensitive adhesive for biomedical electrodes and
transdermal devices.
[0015] U.S. Pat. No. 5,206,071 describes acrylic graft copolymers
and water soluble polymers.
[0016] EP 0716929A1 describes acrylic graft copolymers and water
soluble polymers.
[0017] DE 19516111A1 describes water soluble copolymers with
crosslinkers.
[0018] U.S. Pat. No. 3,813,695 discloses a rubber or latex surgical
glove that is laminated with an internal plastic lining of a
hydrophilic material.
[0019] U.S. Pat. No. 4,575,476 discloses a dipped rubber glove
having an outer rubber layer and a lubricating layer formed of a
hydrogel polymer bonded thereto to provide a skin-contacting
surface of the glove.
BRIEF SUMMARY OF THE INVENTION
[0020] In general, the present invention relates to providing a
cost-effective method for the preparation of gel-free, hydrophilic
polymers, which have utility in topical skin applications, as
cosmetic compositions, dermatological compositions, and as skin
friendly coatings; as pressure sensitive adhesives; and as
precursors for hydrogels.
[0021] The present invention provides a method for the preparation
of a water insoluble, gel-free copolymer of 2-hydroxyethyl
methacrylate and acrylic acid or methacrylic acid substantially in
the absence of a chain transfer agent comprising: introducing
monomeric 2-hydroxyethyl methacrylate containing ethylene glycol
dimethacrylate impurities up to about 0.15% by weight, based on the
weight of the monomer, and at least one of acrylic acid or
methacrylic acid into a solution of water and alcohol; and
copolymerizing the 2-hydroxyethyl methacrylate and the at least one
of acrylic acid or methacrylic acid to form a polymerization
mixture.
[0022] In one embodiment, the monomeric 2-hydroxyethyl methacrylate
useful in the inventive method may contain ethylene glycol
dimethacrylate impurity in the range of about 0.05% to about 0.1%
by weight of the monomer. In another embodiment, the inventive
method uses a monomeric 2-hydroxyethyl methacrylate that contains
impurities in a total amount of no more than about 3% by weight of
the monomer, where the impurities include ethylene glycol
dimethacrylate, diethylene glycol monomethacrylate, methacrylic
acid and mixtures of these impurities.
[0023] Hydrophilic pressure sensitive adhesives are provided by
adding polyalkylene glycol to the polymerization mixture. Flexible
skin coatings are provided by adding a flexiblizing agent to the
polymerization mixture.
[0024] The present invention also provides a method for the
preparation of a hydrophilic, gel-free, water insoluble copolymer
of 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate and at
least one of acrylic acid or methacrylic acid substantially in the
absence of a chain transfer agent comprising: introducing monomeric
2-hydroxyethyl methacrylate, monomeric 4-hydroxybutyl acrylate and
at least one of acrylic acid or methacrylic acid into a solution of
water and alcohol, wherein the monomeric 2-hydroxyethyl
methacrylate contains ethylene glycol dimethacrylate impurities up
to about 0.15% by weight, based on the weight of the monomer; and
copolymerizing the monomeric 2-hydroxyethyl methacrylate, monomeric
4-hydroxybutyl acrylate and at least one of acrylic acid or
methacrylic acid to form a polymerization mixture.
[0025] In another embodiment, the monomeric 2-hydroxyethyl
methacrylate useful in the inventive method contain ethylene glycol
dimethacrylate impurity in the range of about 0.05% to about 0.1%
by weight of the monomer. In another embodiment, the inventive
method uses a monomeric 2-hydroxyethyl methacrylate that contains
impurities in a total amount of no more than about 3% by weight of
the monomer, where the impurities include ethylene glycol
dimethacrylate, diethylene glycol monomethacrylate, methacrylic
acid and mixtures of these impurities.
[0026] Hydrophilic pressure sensitive adhesives are provided by
adding polyalkylene glycol to the polymerization mixture. Flexible
skin coatings are provided by adding a flexiblizing agent to the
polymerization mixture.
[0027] The present invention also provides a method for the
preparation of a substantially monoalcohol-free, gel-free, water
insoluble, hydrophilic copolymer of 2-hydroxyethyl methacrylate and
4-hydroxybutyl acrylate substantially in the absence of a chain
transfer agent comprising: introducing monomeric 2-hydroxyethyl
methacrylate containing ethylene glycol dimethacrylate impurities
up to about 0.15% by weight, based on the weight of the monomer,
and monomeric 4-hydroxybutyl acrylate into a solution of water and
a monoalcohol; copolymerizing the monomeric 2-hydroxyethyl
methacrylate and the 4-hydroxybutyl acrylate to form a
polymerization mixture; leaching the copolymer of 2-hydroxyethyl
methacrylate and 4-hydroxybutyl acrylate to substantially remove
residual monomer; and substantially replacing the monoalcohol with
a polyhydric alcohol.
[0028] In another embodiment, the monomeric 2-hydroxyethyl
methacrylate that is useful in the inventive method may contain
ethylene glycol dimethacrylate impurity in the range of about 0.05%
to about 0.1% by weight of the monomer. In another embodiment, the
inventive method uses a monomeric 2-hydroxyethyl methacrylate that
contains impurities in a total amount of no more than about 3% by
weight of the monomer, where the impurities include ethylene glycol
dimethacrylate, diethylene glycol monomethacrylate, methacrylic
acid and mixtures of these impurities.
[0029] Flexible skin coatings are provided by removing the water
after the leaching and replacing steps.
[0030] The invention further provides a method for the preparation
of a substantially monoalcohol-free, gel-free, water insoluble,
hydrophilic copolymer of 2-hydroxyethyl methacrylate and
4-hydroxybutyl acrylate substantially in the absence of a chain
transfer agent comprising: introducing monomeric 2-hydroxyethyl
methacrylate containing ethylene glycol dimethacrylate impurities
up to about 0.15% by weight, based on the weight of the monomer,
and monomeric 4-hydroxybutyl acrylate into a solution of water and
polyhydric alcohol; and copolymerizing the monomeric 2-hydroxyethyl
methacrylate and the 4-hydroxybutyl acrylate to form a
polymerization mixture.
[0031] In another embodiment, the monomeric 2-hydroxyethyl
methacrylate that is useful in the inventive method may contain
ethylene glycol dimethacrylate impurity in the range of about 0.05%
to about 0.1% by weight of the monomer. In another embodiment, the
inventive method uses a monomeric 2-hydroxyethyl methacrylate that
contains impurities in a total amount of no more than about 3% by
weight of the monomer, where the impurities include ethylene glycol
dimethacrylate, diethylene glycol monomethacrylate, methacrylic
acid and mixtures of these impurities.
[0032] Flexible skin coatings are provided by substantially
removing the water from the polymerization mixture.
[0033] The invention further provides a method for the preparation
of a substantially monoalcohol-free, gel-free, water insoluble,
hydrophilic homopolymer of 2-hydroxyethyl methacrylate
substantially in the absence of a chain transfer agent comprising:
introducing monomeric 2-hydroxyethyl methacrylate containing
ethylene glycol dimethacrylate impurities up to about 0.15% by
weight, based on the weight of the monomer, into a solution of
water and a monoalcohol; polymerizing the 2-hydroxyethyl
methacrylate to form a polymerization mixture; leaching the
homopolymer of 2-hydroxyethyl methacrylate to substantially remove
residual monomer; and substantially replacing the monoalcohol with
a polyhydric alcohol.
[0034] In another embodiment, the monomeric 2-hydroxyethyl
methacrylate that is useful in the inventive method may contain
ethylene glycol dimethacrylate impurity in the range of about 0.05%
to about 0.1% by weight of the monomer. In another embodiment, the
inventive method uses a monomeric 2-hydroxyethyl methacrylate that
contains impurities in a total amount of no more than about 3% by
weight of the monomer, where the impurities include ethylene glycol
dimethacrylate, diethylene glycol monomethacrylate, methacrylic
acid and mixtures of these impurities.
[0035] Flexible skin coatings are provided by substantially
removing the water from the polymer after the leaching and
replacing steps.
[0036] The present invention further provides a method for the
preparation of substantially gel-free, water insoluble, hydrophilic
homopolymer of 2-hydroxyethyl methacrylate substantially in the
absence of a chain transfer agent comprising: introducing monomeric
2-hydroxyethyl methacrylate containing ethylene glycol
dimethacrylate impurities up to about 0.15% by weight, based on the
weight of the monomer, into a solution of water and polyhydric
alcohol; and polymerizing the 2-hydroxyethyl methacrylate to form a
polymerization mixture.
[0037] As such, this invention relates to the method of preparing
gel-free, hydrophilic, water insoluble homopolymers and copolymers,
and gel-free, hydrophilic water soluble copolymers that are
suitable in the formulation of topical compositions for application
to human skin and hair, such as cosmetic compositions and
dermatological compositions, and to their use as pressure sensitive
adhesives and flexible coatings.
DETAILED DESCRIPTION OF THE INVENTION
[0038] The present invention involves processes for the preparation
of gel-free, water insoluble copolymers that can be subsequently
converted to gel-free, hydrophilic, water soluble copolymers by pH
adjustment. The copolymer products of the present invention can be
prepared from an inexpensive industrial or technical grade
2-hydroxyethyl methacrylate monomer source that contains low levels
of ethylene glycol dimethacrylate impurity.
[0039] The gel-free, water insoluble copolymers of the present
invention can be subjected to a leaching process to substantially
remove residual unreacted monomer from the copolymerization mixture
to achieve a copolymer product having even lower residual monomer
content. While the copolymers of the present invention have many
uses, the copolymer products having low residual monomer content
are especially useful in the formulation of cosmetic products for
application to the skin and hair, and of dermatological products
for use in skin and hair care applications.
[0040] The term "gel free" as used in the specification is intended
to be synonymous with the phrases "soluble in alcohol" or
"insoluble in water." The presence or absence of gel in the polymer
products of the present invention can be determined by visually
inspecting the polymerization mixture for the presence of
particulates. Optionally, a thin film of the polymer product can be
poured and visually inspected for particulates. A polymer product
containing no particulate matter upon visual inspection is
considered to be "gel-free."
[0041] In one embodiment, the present invention provides a method
for the preparation of a gel-free, water insoluble copolymer of
2-hydroxyethyl methacrylate and acrylic acid or methacrylic acid
substantially in the absence of a chain transfer agent. The method
of producing the gel-free copolymer includes introducing monomeric
2-hydroxyethyl methacrylate containing ethylene glycol
dimethacrylate impurities up to about 0.15% by weight of the
monomer, and at least one of acrylic acid or methacrylic acid into
a solution of water and alcohol. The monomeric 2-hydroxyethyl
methacrylate and monomeric acrylic acid and/or methacrylic acid are
polymerized to form a polymerization mixture containing a copolymer
of 2-hydroxyethyl methacrylate and acrylic acid and/or methacrylic
acid.
[0042] The method of preparing the gel-free, water insoluble
copolymer of 2-hydroxyethyl methacrylate and acrylic acid and/or
methacrylic acid can utilize monomeric 2-hydroxyethyl methacrylate
containing ethylene glycol dimethacrylate impurities in the range
of about 0.05% to about 0.1%, by weight of the 2-hydroxyethyl
methacrylate monomer.
[0043] The method of preparing the gel-free, water insoluble
copolymer of 2-hydroxyethyl methacrylate and acrylic acid and/or
methacrylic acid may also utilize monomeric 2-hydroxyethyl
methacrylate that contains impurities in a total amount of no more
than about 3% by weight of the monomer, where the impurities
include ethylene glycol dimethacrylate, diethylene glycol
monomethacrylate, methacrylic acid and mixtures of these
impurities.
[0044] The method of the present invention, therefore, provides for
the cost effective preparation of a gel-free 2-hydroxyethyl
methacrylate copolymers using industrial grade 2-hydroxyethyl
methacrylate monomer. A 2-hydroxyethyl methacrylate monomer that is
particularly suitable for use in the method of the present
invention is available from Mitsubishi Rayon, Japan. This
2-hydroxyethyl methacrylate monomer contains less than 0.15% by
weight of ethylene glycol dimethacrylate impurity, based on the
weight of the monomer. The controlled level of impurities in the
2-hydroxyethyl methacrylate monomer results in a gel-free polymer,
without the need for using a very expensive, ultra-pure
2-hydroxyethyl methacrylate monomer source.
[0045] 2-Hydroxyethyl methacrylate monomer suitable for use in the
method of the present invention may also be made by blending
industrial grade 2-hydroxyethyl methacrylate monomer from various
sources to provide the desired level of impurities. Although less
economical, 2-hydroxyethyl methacrylate monomer suitable for use in
the method of the present invention may also be made by adding
specified amounts of impurities to a higher purity 2-hydroxyethyl
methacrylate monomer, to control the properties desired.
[0046] As described above, the copolymer of 2-hydroxyethyl
methacrylate and acrylic or methacrylic acid is prepared in a
solution of alcohol and water. The alcohol used in the inventive
method may include C.sub.1-C.sub.4 lower alcohols. Preferably, the
alcohol used in the copolymerization of 2-hydroxyethyl methacrylate
and acrylic acid and/or methacrylic acid, according to the
inventive method, is ethanol.
[0047] The method for the preparation of a gel-free, water
insoluble copolymer of 2-hydroxyethyl methacrylate and methacrylic
or acrylic acid occurs substantially in the absence of a chain
transfer agent. Polymerization is induced by free radical
initiation using a suitable free radical polymerization initiator.
The initiator preferably should be soluble in alcohol, water and
the monomer mixture. The initiator is added to the alcohol/water
solution containing the mixture of the monomeric 2-hydroxyethyl
methacrylate and acrylic or methacrylic acid in an amount effective
to initiate copolymerization. Suitable initiators include
dissociative initiators and redox initiators. Suitable dissociative
initiators that may be used in the present invention include, but
are not limited to, persulfates such as ammonium persulfate,
potassium persulfate and sodium persulfate, hydrogen peroxide,
tert-butyl hydroperoxide, and azo compounds such as
4,4'-azobis(4-cyanovaleric acid). Redox initiators include, but are
not limited to, persulfates with bisulfite, such as sodium
persulfate with sodium metabisulfite, hydrogen peroxide with
ferrous ion, sulfite ion, bisulfite ion or ascorbic acid, and
hydroperoxides with sulfoxylates, such as tert-butyl hydroperoxide
with sodium formaldehyde sulfoxylate.
[0048] The gel-free, water insoluble copolymer of 2-hydroxyethyl
methacrylate and acrylic or methacrylic acid may be subjected to a
conventional leaching process to remove unreacted, residual monomer
from the polymerization mixture. Typically, a desired amount of
water is added to the polymerization mixture to precipitate the
copolymer product. The effluent forms on the surface of the
copolymer product and is easily decanted off. Thereafter, the
copolymer product may be redissolved with a suitable diluent and
then precipitated again. The diluents that can be used to
redissolve the copolymer product preferably include, but are not
limited to, lower alcohols, alkylene glycols and polyalkylene
glycols. Preferably, ethanol and polypropylene glycol are used to
redissolve the copolymer product during the leaching process.
[0049] The gel-free, water insoluble, leached copolymer of
2-hydroxyethyl methacrylate and acrylic or methacrylic acid is
converted to a hydrophilic, gel-free, water soluble copolymer by pH
adjustment with a suitable base. According to the present
invention, the water insoluble copolymer can be converted to a
water soluble copolymer by adjusting the pH of the copolymer to a
pH of greater than about 4.5. Preferably, the pH of the copolymer
is adjusted to a pH in the range of about 5.5 to about 7.5.
Suitable bases that can be used to adjust the pH of the
copolymerization mixture include, but are not limited to,
hydroxides such as ammonium hydroxide, potassium hydroxide, sodium
hydroxide and alcohol amines, such as triethanolamine.
[0050] In another embodiment, the present invention provides a
method for the preparation of a pressure sensitive adhesive
formulation. The method includes preparing a gel-free, water
insoluble copolymer of 2-hydroxyethyl methacrylate and acrylic or
methacrylic acid. The method utilizes monomeric 2-hydroxyethyl
methacrylate containing ethylene glycol dimethacrylate impurity up
to about 0.15 weight %, based on the weight of the monomer, to
prepare a copolymer of 2-hydroxyethyl methacrylate and acrylic or
methacrylic acid. The monomeric 2-hydroxyethyl methacrylate that is
useful in the inventive method may contain ethylene glycol
dimethacrylate impurity in the range of about 0.05% to about 0.1%
by weight of the monomer. Furthermore, the 2-hydroxyethyl
methacrylate contains alkylene glycol methacrylate impurities in
the range of about 3%, based on the weight of the monomer.
Preferably, the alkylene glycol impurities are selected from the
group consisting of ethylene glycol dimethacrylate, diethylene
glycol monomethacrylate, methacrylic acid and mixtures thereof, in
a total amount of no more than about 3% by weight of monomer.
[0051] The copolymer is then leached as described above. A
polyalkylene glycol is then added to the copolymerization mixture,
and the alcohol and water is substantially removed from the
polymerization mixture to form a hydrophilic pressure sensitive
adhesive. Suitable polyalkylene glycols that can be added to the
copolymerization mixture to form the pressure sensitive adhesive
include polyethylene glycol, polypropylene glycol and copolymers of
polyethylene glycol and polypropylene glycol. Preferably, the
polyalkylene glycol used to prepare the pressure sensitive adhesive
is polyethylene glycol. The polyalkylene glycol, such as
polyethylene glycol, can be added to the copolymerization mixture
in an amount ranging from about 40% to about 70% by weight, based
on the weight of the copolymer and the polyalkylene glycol.
Furthermore, the pH of the copolymer product can be adjusted, as
described above, to render the copolymer product water soluble
prior to the addition of the polyalkylene to the polymerization
mixture. The hydrophilic pressure sensitive adhesives formed by
this method have utility in many label and tape applications, and
is particularly suitable for medical applications.
[0052] In a further embodiment, the present invention provides a
method for the preparation of a flexible hydrophilic coating
including a gel-free copolymer of 2-hydroxyethyl methacrylate and
one of acrylic or methacrylic acid, produced substantially in the
absence of a chain transfer agent. The method comprises introducing
monomeric 2-hydroxyethyl methacrylate containing ethylene glycol
dimethacrylate impurities up to about 0.15 weight %, based on the
weight of the monomer into a solution of alcohol and water. The
monomers are copolymerized to form a polymerization mixture. The
polymerization mixture is then leached to remove residual monomer.
A suitable flexiblizing agent is added to the copolymerization
mixture to impart a flexibility property to the copolymer, and then
the alcohol and water is removed to form a hydrophilic, flexible
coating. Suitable flexiblizing agents include, for example,
alkylene glycols and glycerin. Preferably, the flexiblizing agents
that are added to the copolymerization mixture to form the flexible
skin coating are propylene glycol and glycerin. The flexiblizing
agent should be added to the copolymerization mixture in amount
sufficient to impart a desired level of flexibility to the
copolymer. Preferably, the flexiblizing agent is added to the
polymerization mixture in an amount ranging from about 10% to about
50% by weight of the polymer, most preferably the flexiblizing
agent is added to the polymerization mixture in amount of about
25%, by weight of the polymer.
[0053] The monomeric 2-hydroxyethyl methacrylate that is useful in
the inventive method may contain ethylene glycol dimethacrylate
impurity in the range of about 0.05% to about 0.1% by weight of the
monomer. Furthermore, the 2-hydroxyethyl methacrylate contains
alkylene glycol methacrylate impurities in the range of about 3%,
based on the weight of the monomer. Preferably, the alkylene glycol
impurities are selected from the group consisting of ethylene
glycol dimethacrylate, diethylene glycol monomethacrylate,
methacrylic acid and mixtures thereof, in a total amount of no more
than about 3% by weight of monomer. Furthermore, the pH of the
copolymer product can be adjusted, as described above, to render
the copolymer product water soluble prior to the addition of the
flexibilizing agent to the polymerization mixture. The flexible
hydrophilic coating formed by this method has utility in
skin-friendly applications in which a high Moisture Vapor
Transmission Rate (MVTR) is needed together with protective, skin
barrier properties. The coating is also suitable for printable
coatings, such as inkjet coatings for paper, plastic film, and the
like.
[0054] In another embodiment, the present invention provides a
method for the preparation of a gel free, water insoluble copolymer
of 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate and acrylic
and/or methacrylic acid. The method includes introducing monomeric
2-hydroxyethyl methacrylate containing up to about 0.15 weight % of
ethylene glycol dimethacrylate impurity, based on the weight of the
monomer, monomeric 4-hydroxybutyl acrylate and monomeric acrylic
and/or methacrylic acid into a solution of alcohol and water, and
copolymerizing these monomers to form a polymerization mixture. The
alcohol is selected from lower alcohols, and is preferably selected
from one of methanol and ethanol. More preferably, the lower
alcohol used is ethanol.
[0055] The method of a preparing the gel free, water insoluble
copolymer of 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate
and acrylic and/or methacrylic acid may include using monomeric
2-hydroxyethyl methacrylate containing 0.05 to 0.1% by weight of
ethylene glycol dimethacrylate impurities, based on the weight of
the monomer.
[0056] The method of preparing the gel free, water insoluble
copolymer of 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate
and acrylic and/or methacrylic acid may include using monomeric
2-hydroxyethyl methacrylate that contains impurities in a total
amount of no more than about 3% by weight of the monomer, where the
impurities include ethylene glycol dimethacrylate, diethylene
glycol monomethacrylate, methacrylic acid and mixtures of these
impurities.
[0057] A 2-hydroxyethyl methacrylate monomer that is particularly
suitable for use in the preparation of a copolymer of
2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate and acrylic
and/or methacrylic acid is available from Mitsubishi Rayon, Japan.
The Mitsubishi 2-hydroxyethyl methacrylate monomer contains less
than 0.15 % by weight of ethylene glycol dimethacrylate impurity,
based on the weight of the monomer. The controlled level of
impurities in the 2-hydroxyethyl methacrylate monomer permits the
preparation of the gel-free polymer, without the need for using a
very expensive, ultra-pure 2-hydroxyethyl methacrylate monomer
source.
[0058] The method for the preparation of a gel-free, water
insoluble copolymer of 2-hydroxyethyl methacrylate, 4-hydroxybutyl
acrylate and methacrylic or acrylic acid occurs substantially in
the absence of a chain transfer agent. Polymerization is induced by
free radical initiation using a suitable free radical
polymerization initiator. The initiator is added to the
alcohol/water solution containing the mixture of the monomeric
2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate and acrylic or
methacrylic acid in an amount effective to initiate
copolymerization. The initiator preferably should be soluble in
alcohol, water and the monomer mixture. Suitable initiators for the
copolymerization of the monomeric 2-hydroxyethyl methacrylate,
4-hydroxybutyl acrylate and acrylic or methacrylic acid that are
soluble in water include, but are not limited to, dissociative
initiators and redox initiators. Suitable dissociative initiators
that may be used in the present invention include, but are not
limited to, persulfates such as ammonium persulfate, potassium
persulfate and sodium persulfate, hydrogen peroxide, tert-butyl
hydroperoxide, and azo compounds such as 4,4'-azobis(4-cyanovaleric
acid). Redox initiators include, but are not limited to,
persulfates with bisulfite, such as sodium persulfate with sodium
metabisulfite, hydrogen peroxide with ferrous ion, sulfite ion,
bisulfite ion or ascorbic acid, and hydroperoxides with
sulfoxylates, such as tert-butyl hydroperoxide with sodium
formaldehyde sulfoxylate.
[0059] The gel-free, water insoluble copolymer of 2-hydroxyethyl
methacrylate, 4-hydroxybutyl acrylate and acrylic or methacrylic
acid may be subjected to a conventional leaching process to
substantially remove unreacted, residual monomer from the
polymerization mixture. Typically, a desired amount of water is
added to the polymerization mixture to precipitate the copolymer
product. The effluent forms on the surface of the copolymer product
and is decanted off. Thereafter, the copolymer product is
redissolved with a suitable diluent, followed by further
precipitation and decanting. The diluents that can be used to
redissolve the copolymer product preferably include, but are not
limited to, lower alcohols, alkylene glycols and polyalkylene
glycols. Preferably, ethanol and polypropylene glycol are used to
redissolve the copolymer product during the leaching process.
[0060] The gel-free, water insoluble, leached copolymer of
2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate and acrylic or
methacrylic acid can be converted to a hydrophilic, gel-free, water
soluble copolymer by pH adjustment with a suitable base. According
to the present invention, the pH of the copolymerization mixture
need only be adjusted to a pH at which the water insoluble
copolymer is converted to a water soluble copolymer. Preferably,
the water insoluble copolymer can be converted to a water soluble
copolymer by adjusting the pH of the copolymer to a pH of greater
than about 4.5. More preferably, the pH of the copolymer can be
adjusted to a pH in the range of about 5.5 to about 7.5. The pH
adjustment of the copolymer can be achieved through the addition of
a suitable base to a water/alcohol solution containing the
copolymer or to a water/alkylene glycol solution containing the
copolymer. Alternatively, the pH of the copolymer can be adjusted
by redissolving the precipitated copolymer with a suitable base.
Suitable bases that can be used to adjust the pH of the copolymer
include, but are not limited to, hydroxides such as ammonium
hydroxide, potassium hydroxide and sodium hydroxide, and alcohol
amines, such as triethanolamine.
[0061] In one embodiment, the present invention provides a method
for the preparation of a pressure sensitive adhesive formulation.
The method includes preparing a gel-free, water insoluble copolymer
of 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate and acrylic
or methacrylic acid. The method utilizes monomeric 2-hydroxyethyl
methacrylate containing ethylene glycol dimethacrylate impurities
up to about 0.15 weight %, based on the weight of the monomer. The
monomeric 2-hydroxyethyl methacrylate that is useful in the
inventive method may contain ethylene glycol dimethacrylate
impurity in the range of about 0.05% to about 0.1% by weight of the
monomer. Furthermore, the 2-hydroxyethyl methacrylate contains
alkylene glycol methacrylate impurities in the range of about 3%,
based on the weight of the monomer. Preferably, the alkylene glycol
impurities are selected from the group consisting of ethylene
glycol dimethacrylate, diethylene glycol monomethacrylate,
methacrylic acid and mixtures thereof, in a total amount of no more
than about 3% by weight of monomer. The monomeric 2-hydroxyethyl
methacrylate, 4-hydroxybutyl acrylate and acrylic or methacrylic
acid are copolymerized to form a polymerization mixture.
[0062] A polyalkylene glycol is then added to the copolymerization
mixture and the alcohol and water is substantially removed to form
a hydrophilic pressure sensitive adhesive. Suitable polyalkylene
glycols that can be added to the copolymer to form the pressure
sensitive adhesive include polyethylene glycol, polypropylene
glycol and copolymers of polyethylene glycol and polypropylene
glycol. Preferably, the polyalkylene glycol used to prepare the
pressure sensitive adhesive is polyethylene glycol. The
polyalkylene glycol, such as polyethylene glycol, can be added to
the copolymerization mixture in an amount ranging from about 40% to
about 70% by weight, based on the weight of the copolymer and the
polyalkylene glycol. Prior to the addition of the polyalkylene
glycol to the polymerization mixture, the copolymer product can be
leached, as described above, to substantially remove residual
monomer. Furthermore, the pH of the copolymer product can be
adjusted to render the copolymer product water soluble before
addition of the polyalkylene glycol to the polymerization mixture.
The hydrophilic pressure sensitive adhesives formed by this method
have utility in many label and tape applications, and is
particularly suitable for medical applications.
[0063] In a further embodiment, the present invention provides a
method for the preparation of a flexible hydrophilic coating
comprising a gel-free copolymer of 2-hydroxyethyl methacrylate,
4-hydroxybutyl acrylate and one of acrylic or methacrylic acid,
produced substantially in the absence of a chain transfer agent.
The method comprises introducing monomeric 2-hydroxyethyl
methacrylate containing ethylene glycol dimethacrylate impurities
up to about 0.15 weight %, based on the weight of the monomer,
monomeric 4-hydroxybutyl acrylate and monomeric acrylic and/or
methacrylic acid into a solution of alcohol and water. The
monomeric 2-hydroxyethyl methacrylate that is useful in the
inventive method may contain ethylene glycol dimethacrylate
impurity in the range of about 0.05% to about 0.1% by weight of the
monomer. Furthermore, the 2-hydroxyethyl methacrylate contains
alkylene glycol methacrylate impurities in the range of about 3%,
based on the weight of the monomer. Preferably, the alkylene glycol
impurities are selected from the group consisting of ethylene
glycol dimethacrylate, diethylene glycol monomethacrylate,
methacrylic acid and mixtures thereof, in a total amount of no more
than about 3% by weight of monomer.
[0064] The monomers are copolymerized to form a polymerization
mixture. A suitable flexiblizing agent is added to the
copolymerization mixture to impart a flexibility property to the
copolymer, and the alcohol and water is removed to for a
hydrophilic, flexible coating. Suitable flexiblizing agents
include, for example, alkylene glycols and glycerin. Preferably,
the flexiblizing agents that are added to the copolymerization
mixture to form the flexible skin coating are propylene glycol and
glycerin. The flexiblizing agent should be added to the
copolymerization mixture in amount sufficient to impart a desired
level of flexibility to the copolymer. Preferably, the flexiblizing
agent is added to the polymerization mixture in an amount ranging
from about 10% to about 50% by weight of the polymer, preferably
the flexiblizing agent is added to the polymerization mixture in
amount of about 25%, by weight of the polymer
[0065] The flexible hydrophilic coating formed by this method has
utility in skin-friendly applications in which a high Moisture
Vapor Transmission Rate (MVTR) is needed together with protective,
skin barrier properties. The coating is also suitable for printable
coatings, such as inkjet coatings for paper, plastic film, and the
like.
[0066] The copolymer of 2-hydroxyethyl methacrylate, 4-hydroxybutyl
acrylate and acrylic and/or methacrylic acid is a hydrophilic
copolymer that, before pH adjustment, is insoluble in water and
does not require crosslinking for water resistance. In addition,
the copolymer of 2-hydroxyethyl methacrylate, 4-hydroxybutyl
acrylate and methacrylic acid is flexible enough to form a flexible
coating or film for medical and skin care or skin protection
applications without the need for the addition of glycerin. The
flexible coating comprising the copolymer of 2-hydroxyethyl
methacrylate, 4-hydroxybutyl acrylate and methacrylic acid is also
useful as a rubber or latex glove coating, with particular
usefulness in wet-donning applications. Rubber or latex gloves
require the ability of donning, that is, the ability to slide a
glove on and off the surface of the skin with minimal friction. The
copolymer of 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate
and methacrylic acid provides a flexible, non-tacky glove coating
that allows the donning, wet or dry, of the rubber or latex glove
with minimal blocking and without undue friction or clinging.
[0067] The present invention, in one embodiment, provides a
gel-free, hydrophilic copolymer of 2-hydroxyethyl methacrylate,
4-hydroxybutyl acrylate and methacrylic acid that does not to be
plasticized. The copolymer of 2-hydroxyethyl methacrylate,
4-hydroxybutyl acrylate and acrylic and/or methacrylic acid, before
pH adjustment, is a water-insoluble, water-absorbing, amphiphilic,
elastic, abrasion resistant and has improved mechanical properties.
It should be noted, however, that while the copolymer of
2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate and
methacrylic acid alone can be flexible enough to form a flexible
skin coating, a desired flexiblizing agent, for example, glycerin
or an alkyl glycol can be added to the copolymer to further enhance
the performance as a skin coating.
[0068] A method for the preparation of hydrophilic, gel-free, water
insoluble copolymer of 2-hydroxyethyl methacrylate and
4-hydroxybutyl acrylate substantially in the absence of a chain
transfer agent is also included in the present invention. According
to this embodiment, the copolymer of 2-hydroxyethyl methacrylate
and 4-hydroxybutyl acrylate is substantially free of monoalcohol.
The method includes introducing monomeric 2-hydroxyethyl
methacrylate containing ethylene glycol dimethacrylate impurities
up to about 0.15% by weight of the monomer and monomeric
4-hydroxybutyl acrylate into a solution of water and a monoalcohol.
The monomeric 2-hydroxyethyl methacrylate and the 4-hydroxybutyl
acrylate are then copolymerized in the solution of water and the
monoalcohol to form a polymerization mixture. The copolymer is
leached to remove residual unreacted monomer. The monoalcohol
present in the leached copolymer product of 2-hydroxyethyl
methacrylate and 4-hydroxybutyl acrylate is substantially replaced
by redissolving the copolymer in a polyhydric alcohol, followed by
further leaching and decanting, to produce a substantially
monoalcohol-free copolymer of 2-hydroxyethyl methacrylate and
4-hydroxybutyl acrylate.
[0069] As used in the specification, the term "monoalcohol" refers
to a monohydric alcohol. Without limitation, the monoalcohol used
in the polymerization process is preferably selected from
monohydric C.sub.1-C.sub.4 alkyl alcohols. More preferably, the
monoalcohol used in the copolymerization of 2-hydroxyethyl
methacrylate and 4-hydroxybutyl acrylate is selected from methanol
and ethanol. The term "polyhydric alcohol" refers to an alcohol
having more than one hydroxyl group and, is intended to encompass
both dihydric alcohols, which have two hydroxyl groups, and
alcohols having more than two hydroxyl groups.
[0070] The method of preparing the gel-free, water insoluble
copolymer of 2-hydroxyethyl methacrylate and 4-hydroxybutyl
acrylate, in another embodiment, can utilize monomeric
2-hydroxyethyl methacrylate containing ethylene glycol
dimethacrylate impurities in the range of about 0.05% to about
0.1%, by weight of the 2-hydroxyethyl methacrylate monomer.
[0071] The method of preparing the gel-free, water insoluble
copolymer of 2-hydroxyethyl methacrylate and 4-hydroxybutyl
acrylate may also utilize monomeric 2-hydroxyethyl methacrylate
that contains impurities in a total amount of no more than about 3%
by weight of the monomer, where the impurities include ethylene
glycol dimethacrylate, diethylene glycol monomethacrylate,
methacrylic acid and mixtures of these impurities.
[0072] The method of forming the gel-free, water insoluble
copolymer of 2-hydroxyethyl methacrylate and 4-hydroxybutyl
acrylate employs the use of an industrial grade 2-hydroxyethyl
methacrylate monomer. A 2-hydroxyethyl methacrylate industrial
grade monomer that is particularly suitable for use in the method
is available from Mitsubishi Rayon, Japan. This 2-hydroxyethyl
methacrylate monomer contains less than about 0.15% by weight of
ethylene glycol dimethacrylate impurity, based on the weight of the
monomer.
[0073] 2-Hydroxyethyl methacrylate monomer suitable for use in the
method of preparing a copolymer of 2-hydroxyethyl methacrylate and
4-hydroxybutyl acrylate may also be made by blending industrial
grade 2-hydroxyethyl methacrylate monomer from various sources to
provide the desired level of impurities. Although less economical,
2-hydroxyethyl methacrylate monomer suitable for use in the method
of the present invention may also be made by adding specified
amounts of impurities to a higher purity 2-hydroxyethyl
methacrylate monomer, to control the properties desired.
[0074] The preparation of a gel-free, water insoluble copolymer of
2-hydroxyethyl methacrylate and 4-hydroxybutyl acrylate occurs
substantially in the absence of a chain transfer agent.
Polymerization is induced by free radical initiation using a
suitable free radical polymerization initiator. The initiator
preferably should be soluble in alcohol, water and the monomer
mixture. The initiator is added to the alcohol/water solution
containing the mixture of the monomeric 2-hydroxyethyl methacrylate
and 4-hydroxybutyl acrylate in an amount effective to initiate
copolymerization. Suitable initiators include dissociative
initiators and redox initiators. Suitable dissociative initiators
that may be used in the present invention include, but are not
limited to, persulfates such as ammonium persulfate, potassium
persulfate and sodium persulfate, hydrogen peroxide, tert-butyl
hydroperoxide, and azo compounds such as 4,4'-azobis(4-cyanovaleric
acid). Redox initiators include, but are not limited to,
persulfates with bisulfite, such as sodium persulfate with sodium
metabisulfite, hydrogen peroxide with ferrous ion, sulfite ion,
bisulfite ion or ascorbic acid, and hydroperoxides with
sulfoxylates, such as tert-butyl hydroperoxide with sodium
formaldehyde sulfoxylate.
[0075] As described above, the gel-free, water insoluble copolymer
of 2-hydroxyethyl methacrylate and 4-hydroxybutyl acrylate may be
subjected to a conventional leaching process to substantially
remove unreacted, residual monomer from the polymerization mixture.
Typically, a desired amount of water is added to the polymerization
mixture to precipitate the copolymer product. The effluent forms on
the surface of the copolymer product and is easily decanted off.
Thereafter, the copolymer product is redissolved with a suitable
diluent, and the redissolved copolymer may be subjected to further
precipitation and decanting. Preferably, polyhydric alcohols are
used to redissolve the copolymer product. Suitable polyhydric
alcohols that can be used to redissolve the copolymer product
include, but are not limited to, alkylene glycols, alkyl ethers of
alkylene glycols, diols, glycerin and alkyl esters of glycerin. By
redissolving the copolymer product in a polyhydric alcohol, the
monoalcohol present in the copolymer product is substantially
replaced by the polyhydric alcohol to produce a substantially
monoalcohol free copolymer of 2-hydroxyethyl methacrylate and
4-hydroxybutyl acrylate.
[0076] The preferred alkylene glycols that can be used include, but
are not limited to ethylene glycol and propylene glycol, with
propylene glycol being more preferred. Where alkyl ethers of
alkylene glycols are used to redissolve the copolymer product, the
alkyl ethers of alkylene glycols may be selected from ethylene
glycol monomethyl ether, ethylene glycol monoethyl ether, propylene
glycol monomethyl ether and propylene glycol monoethyl ether.
Furthermore, diols may be used to redissolve the copolymer product
of 2-hydroxyethyl methacrylate and 4-hydroxybutyl acrylate.
Suitable diols that may be utilized include, but are not limited
to, 1,3-butanediol, 1,4-butanediol, 2-methyl-2,4-pentanediol,
2,5-hexanediol and 2,4-heptanediol. Glycerin and alkyl esters of
glycerin may be utilized to redissolve the copolymer product of
2-hydroxyethyl methacrylate and 4-hydroxybutyl acrylate. If
utilized, the alkyl esters of glycerin may include glycerin
monolaurate, glycerin monooleate and glycerin monostearate.
Preferably, polypropylene glycol or glycerin are used to redissolve
the copolymer product.
[0077] The invention also includes a method for the preparation of
substantially monoalcohol-free, gel-free, water insoluble,
hydrophilic copolymer of 2hydroxyethyl methacrylate and
4-hydroxybutyl acrylate substantially in the absence of a chain
transfer agent comprising. The method, according this embodiment,
includes introducing monomeric 2-hydroxyethyl methacrylate
containing ethylene glycol dimethacrylate impurities up to about
0.15% by weight, based on the weight of the monomer, and monomeric
4-hydroxybutyl acrylate into a solution of water and polyhydric
alcohol. The monomeric 2-hydroxyethyl methacrylate and the
4-hydroxybutyl acrylate are copolymerized in the solution of water
and polyhydric alcohol to form a polymerization mixture containing
the copolymer.
[0078] The polyhydric alcohol in which the copolymerization of
2-hydroxethyl methacrylate and 4-hydroxybutyl acrylate occurs
includes, but is not limited to, alkylene glycols, alkyl ethers of
alkylene glycols, diols, glycerin and alkyl esters of glycerin. The
copolymer may be leached, preferably with water, to remove residual
monomer. The polyhydric alcohol may be replaced by a monoalcohol by
redissolving the copolymer in a monoalcohol, followed by leaching
and decanting.
[0079] The present invention includes a method for the preparation
of a pressure sensitive adhesive including the copolymer of
2-hydroxyethyl methacrylate and 4-hydroxybutyl acrylate. The method
includes preparing a gel-free, water insoluble copolymer of
2-hydroxyethyl methacrylate and 4-hydroxybutyl acrylate. The method
utilizes monomeric 2-hydroxyethyl methacrylate containing ethylene
glycol dimethacrylate impurity up to about 0.15 weight %, based on
the weight of the monomer, to prepare a copolymer of 2-hydroxyethyl
methacrylate and 4-hydroxybutyl acrylate. The copolymer is then
leached as described above. A polyalkylene glycol is then added to
the copolymerization mixture, and the alcohol and water is
substantially removed from the polymerization mixture to form a
hydrophilic pressure sensitive adhesive. Suitable polyalkylene
glycols that can be added to the copolymerization mixture to form
the pressure sensitive adhesive include polyethylene glycol,
polypropylene glycol and copolymers of polyethylene glycol and
polypropylene glycol. Preferably, the polyalkylene glycol used to
prepare the pressure sensitive adhesive is polyethylene glycol. The
polyalkylene glycol, such as polyethylene glycol, can be added to
the copolymerization mixture in an amount ranging from about 40% to
about 70% by weight, based on the weight of the copolymer and the
polyalkylene glycol. The hydrophilic pressure sensitive adhesives
formed by this method have utility in many label and tape
applications, and is particularly suitable for medical
applications.
[0080] The method of preparing the pressure sensitive adhesive
including the gel-free, water insoluble copolymer of 2-hydroxyethyl
methacrylate and 4-hydroxybutyl acrylate can also utilize monomeric
2-hydroxyethyl methacrylate containing ethylene glycol
dimethacrylate impurities in the range of about 0.05% to about
0.1%, by weight of the 2-hydroxyethyl methacrylate monomer.
[0081] The method of preparing the pressure sensitive adhesive
including the gel-free, water insoluble copolymer of 2-hydroxyethyl
methacrylate and 4-hydroxybutyl acrylate may further utilize
monomeric 2-hydroxyethyl methacrylate that contains impurities in a
total amount of no more than about 3% by weight of the monomer,
where the impurities include ethylene glycol dimethacrylate,
diethylene glycol monomethacrylate, methacrylic acid and mixtures
of these impurities.
[0082] The present invention also provides a method for the
preparation of a flexible hydrophilic coating including a gel-free,
water insoluble copolymer of 2-hydroxyethyl methacrylate and
4-hydroxybutyl acrylate, produced substantially in the absence of a
chain transfer agent. The method comprises introducing monomeric
2-hydroxyethyl methacrylate containing ethylene glycol
dimethacrylate impurities up to about 0.15 weight %, based on the
weight of the monomer into a solution of alcohol and water.
[0083] The monomers are copolymerized to form a polymerization
mixture. The polymerization mixture is then leached to remove
residual monomer. A suitable flexiblizing agent is added to the
copolymerization mixture to impart a flexibility property to the
copolymer, and then the alcohol and water is removed to form a
hydrophilic, flexible coating. Suitable flexiblizing agents
include, for example, alkylene glycols and glycerin. Preferably,
the flexiblizing agents that are added to the copolymerization
mixture to form the flexible skin coating are propylene glycol and
glycerin. The flexiblizing agent should be added to the
copolymerization mixture in amount sufficient to impart a desired
flexiblizing property to the copolymer. Preferably, the
flexiblizing agent is added to the polymerization mixture in an
amount ranging from about 10% to about 50% by weight of the
polymer, most preferably the flexiblizing agent is added to the
polymerization mixture in amount of about 25%, by weight of the
polymer. It should be noted, however, that while the copolymer of
2-hydroxyethyl methacrylate, and 4-hydroxybutyl acrylate alone can
be flexible enough to form a flexible skin coating, a desired
flexiblizing agent, for example, glycerin or an alkylene glycol can
be added to the copolymer to further enhance the performance as a
skin coating.
[0084] A method for the preparation of substantially
monoalcohol-free, gel-free, water insoluble, hydrophilic
homopolymer of 2-hydroxyethyl methacrylate substantially in the
absence of a chain transfer agent is also provided. The method
comprises introducing monomeric 2-hydroxyethyl methacrylate
containing ethylene glycol dimethacrylate impurities up to about
0.15% by weight, based on the weight of the monomer, into a
solution of water and a monoalcohol. The monomeric 2-hydroxyethyl
methacrylate is polymerized to form a polymerization mixture
containing the homopolymer. The homopolymer of 2-hydroxyethyl
methacrylate may be leached to substantially remove residual
monomer, followed by substantially replacing the monoalcohol with a
polyhydric alcohol.
[0085] The same polyhydric alcohols used to redissolve the
copolymer of 2-hydroxyethyl methacrylate and 4-hydroxybutyl
acrylate and to substantially replace the monoalcohol in that
copolymer can be used to redissolve the homopolymer of
2-hydroxyethyl methacrylate and to substantially replace the
monoalcohol present in the homopolymer.
[0086] The method of preparing the gel-free, hydrophilic, water
insoluble polymer of 2-hydroxyethyl methacrylate, in another
embodiment, can utilize monomeric 2-hydroxyethyl methacrylate
containing ethylene glycol dimethacrylate impurities in the range
of about 0.05% to about 0.1%, by weight of the 2-hydroxyethyl
methacrylate monomer.
[0087] The method of preparing the gel-free, hydrophilic, water
insoluble polymer of 2-hydroxyethyl methacrylate may also utilize
monomeric 2-hydroxyethyl methacrylate that contains impurities in a
total amount of no more than about 3% by weight of the monomer,
where the impurities include ethylene glycol dimethacrylate,
diethylene glycol monomethacrylate, methacrylic acid and mixtures
of these impurities.
[0088] The method of forming the gel-free, water insoluble polymer
of 2-hydroxyethyl methacrylate employs the use of an industrial
grade 2-hydroxyethyl methacrylate monomer. A 2-hydroxyethyl
methacrylate industrial grade monomer that is particularly suitable
for use in the method is available from Mitsubishi Rayon, Japan.
This 2-hydroxyethyl methacrylate monomer contains less than 0.15%
by weight of ethylene glycol dimethacrylate impurity, based on the
weight of the monomer. 2-Hydroxyethyl methacrylate monomer suitable
for use in the method of preparing a homopolymer of 2-hydroxyethyl
methacrylate may also be made by blending industrial grade
2-hydroxyethyl methacrylate monomer from various sources to provide
the desired level of impurities. Although less economical,
2-hydroxyethyl methacrylate monomer suitable for use in the method
of the present invention may also be made by adding specified
amounts of impurities to a higher purity 2-hydroxyethyl
methacrylate monomer, to control the properties desired.
[0089] A method for the preparation of gel-free, hydrophilic
homopolymer of 2-hydroxyethyl methacrylate substantially in the
absence of a chain transfer agent is also included in the present
invention. The method includes introducing monomeric 2-hydroxyethyl
methacrylate containing ethylene glycol dimethacrylate impurities
up to about 0.15% by weight into a solution of water and a
polyhydric alcohol. The 2-hydroxyethyl methacrylate is then
polymerized to form a polymerization mixture containing the
homopolymer.
[0090] The method of preparing the gel-free, hydrophilic, water
insoluble polymer of 2-hydroxyethyl methacrylate, in another
embodiment, can utilize monomeric 2-hydroxyethyl methacrylate
containing ethylene glycol dimethacrylate impurities in the range
of about 0.05% to about 0.1%, by weight of the 2-hydroxyethyl
methacrylate monomer.
[0091] The method of preparing the gel-free, hydrophilic, water
insoluble polymer of 2-hydroxyethyl methacrylate may also utilize
monomeric 2-hydroxyethyl methacrylate that contains impurities in a
total amount of no more than about 3% by weight of the monomer,
where the impurities include ethylene glycol dimethacrylate,
diethylene glycol monomethacrylate, methacrylic acid and mixtures
of these impurities.
[0092] The method of forming the gel-free, water insoluble polymer
of 2-hydroxyethyl methacrylate employs the use of an industrial
grade 2-hydroxyethyl methacrylate monomer. A 2-hydroxyethyl
methacrylate industrial grade monomer that is particularly suitable
for use in the method is available from Mitsubishi Rayon, Japan.
This 2-hydroxyethyl methacrylate monomer contains less than 0.15%
by weight of ethylene glycol dimethacrylate impurity, based on the
weight of the monomer.
[0093] 2-Hydroxyethyl methacrylate monomer suitable for use in the
method of preparing a homopolymer of 2-hydroxyethyl methacrylate
may also be made by blending industrial grade 2-hydroxyethyl
methacrylate monomer from various sources to provide the desired
level of impurities. Although less economical, 2-hydroxyethyl
methacrylate monomer suitable for use in the method of the present
invention may also be made by adding specified amounts of
impurities to a higher purity 2-hydroxyethyl methacrylate monomer,
to control the properties desired.
[0094] The polyhydric alcohol in which the copolymerization of
2-hydroxethyl methacrylate and 4-hydroxybutyl acrylate occurs
includes, but is not limited to, alkylene glycols, alkyl ethers of
alkylene glycols, diols, glycerin and alkyl esters of glycerin.
[0095] The preparation of a gel-free, water insoluble homopolymer
of 2-hydroxyethyl methacrylate occurs substantially in the absence
of a chain transfer agent. Polymerization is induced by free
radical initiation using a suitable free radical polymerization
initiator. The initiator preferably should be soluble in alcohol,
water and the monomer. The initiator is added to the alcohol/water
solution containing the monomeric 2-hydroxyethyl methacrylate in an
amount effective to initiate polymerization. Suitable initiators
include dissociative initiators and redox initiators. Suitable
dissociative initiators that may be used in the present invention
include, but are not limited to, persulfates such as ammonium
persulfate, potassium persulfate and sodium persulfate, hydrogen
peroxide, tert-butyl hydroperoxide, and azo compounds such as
4,4'-azobis(4-cyanovaleric acid). Redox initiators include, but are
not limited to, persulfates with bisulfite, such as sodium
persulfate with sodium metabisulfite, hydrogen peroxide with
ferrous ion, sulfite ion, bisulfite ion or ascorbic acid, and
hydroperoxides with sulfoxylates, such as tert-butyl hydroperoxide
with sodium formaldehyde sulfoxylate.
[0096] The gel-free, water insoluble homopolymer of 2-hydroxyethyl
methacrylate may subjected to a conventional leaching process to
substantially remove unreacted, residual monomer from the
polymerization mixture. Typically, a desired amount of water is
added to the polymerization mixture to precipitate the polymer
product. The effluent forms on the surface of the polymer product
and is easily decanted off. Thereafter, the polymer product is
redissolved with a suitable diluent, and the redissolved polymer
can be subjected to further precipitation and decanting. The
diluents that can be used to redissolve the polymer product
preferably include, but are not limited to, lower alcohols,
alkylene glycols and polyalkylene glycols. Preferably, ethanol and
polypropylene glycol are used to redissolve the polymer product
during the leaching process. Furthermore, the polyhydric alcohol
can be substantially replaced with a monohydric alcohol by
redissolving the homopolymer in a monohydric alcohol, followed by
further leaching and decanting to drive off the polyhydric alcohol,
thus resulting in a copolymer product containing the monohydric
alcohol.
[0097] The present invention includes a method for the preparation
of a pressure sensitive adhesive including the homopolymer of
2-hydroxyethyl methacrylate. The method includes preparing a
gel-free, water insoluble homopolymer of 2-hydroxyethyl
methacrylate. The method utilizes monomeric 2-hydroxyethyl
methacrylate containing ethylene glycol dimethacrylate impurity up
to about 0.15 weight %, based on the weight of the monomer, to
prepare a homopolymer of 2-hydroxyethyl methacrylate. The
homopolymer is then leached as described above to substantially
remove residual monomer. A polyalkylene glycol is then added to the
polymerization mixture, and the alcohol and water is substantially
removed from the polymerization mixture to form a hydrophilic
pressure sensitive adhesive. Suitable polyalkylene glycols that can
be added to the polymerization mixture to form the pressure
sensitive adhesive include polyethylene glycol, polypropylene
glycol and copolymers of polyethylene glycol and polypropylene
glycol. Preferably, the polyalkylene glycol used to prepare the
pressure sensitive adhesive is polyethylene glycol. The
polyalkylene glycol, such as polyethylene glycol, can be added to
the polymerization mixture in an amount ranging from about 40% to
about 70% by weight, based on the weight of the copolymer and the
polyalkylene glycol. The hydrophilic pressure sensitive adhesives
formed by this method have utility in many label and tape
applications, and is particularly suitable for medical
applications.
[0098] The present invention also provides a method for the
preparation of a flexible hydrophilic coating including a gel-free,
water insoluble homopolymer of 2-hydroxyethyl methacrylate,
produced substantially in the absence of a chain transfer agent.
The method comprises introducing monomeric 2-hydroxyethyl
methacrylate containing ethylene glycol dimethacrylate impurities
up to about 0.15 weight %, based on the weight of the monomer into
a solution of alcohol and water. The monomer is polymerized to form
a polymerization mixture. The polymerization mixture is then
leached to substantially remove residual monomer. A suitable
flexiblizing agent is added to the copolymerization mixture to
impart a flexibility property to the homopolymer, and then the
alcohol and water is removed to form a hydrophilic, flexible
coating. Suitable flexiblizing agents include, for example,
alkylene glycols and glycerin. Preferably, the flexiblizing agents
that are added to the polymerization mixture to form the flexible
skin coating are propylene glycol and glycerin. The flexiblizing
agent should be added to the polymerization mixture in amount
sufficient to impart a desired flexiblizing property to the
homopolymer. Preferably, the flexiblizing agent is added to the
polymerization mixture in an amount ranging from about 10% to about
50% by weight of the homopolymer, most preferably the flexiblizing
agent is added to the polymerization mixture in amount of about
25%, by weight of the polymer.
[0099] The copolymer product of 2-hydroxyethyl methacrylate and
acrylic and/or methacrylic acid, the copolymer product of
2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate and acrylic
and/or methacrylic acid, the copolymer of 2-hydroxyethyl
methacrylate and 4-hydroxybutyl acrylate, and the homopolymer of
2-hydroxyethyl methacrylate may further contain up to about 10
weight percent of an additional monomer, based on the weight of the
polymeric product. More preferably, the polymeric product may
contain from about 2 to about 4 weight percent of the additional
monomer. The inclusion of up to about 10 weight percent of the
additional monomer increases the cohesive strength of the polymer
product, while still maintaining pressure sensitive adhesive
properties, skin coating properties, and water resistance. Useful
monomers that may be added to the polymer products of the present
invention include, for example, alkyl acrylates, alkyl
methacrylates, hydroxyalkyl acrylates, hydroxyalkyl methacrylates,
fluorinated alkyl acrylates, including 1H, 1H-triflouroethyl
acrylate, 1H, 1H-heptaflourobutyl acrylate and 1H,
1H-pentadecaflourooctyl acrylate, fluorinated alkyl methacrylates
including 1H, 1H-triflouroethyl methacrylate, 1H,
1H-heptaflourobutyl methacrylate and 1H, 1H-pentadecaflourooctyl
methacrylate, N-vinyl lactam, dimethylaminoethyl acrylate,
methylene chloride quaternary salt of dimethylaminoethyl acrylate,
diethylaminoethyl acrylate, methylene chloride quaternary salt of
diethylaminoethyl acrylate, dimethylaminoethyl methacrylate,
methylene chloride quaternary salt of dimethylaminoethyl
methacrylate, diethylaminoethyl methacrylate, methylene chloride
quaternary salt of diethylaminoethyl methacrylate, vinyl acetate
and styrene monomers. The alkyl component of the above monomers is
preferably a C.sub.1-C.sub.17 alkyl group.
[0100] The copolymer of 2-hydroxyethyl methacrylate and acrylic
and/or methacylic acid, or the copolymer of 2-hydroxyethyl
methacrylate, 4-hydroxybutyl acrylate, and acrylic and/or
methacrylic acid can utilize other polymerizable acid monomers
besides acrylic acid and methacrylic acid. Non-limiting examples of
other polymerizable acid monomers include, but are not limited to,
b-carboxyethyl acrylate, crotonic acid, maleic acid, fumaric acid,
and itaconic acid.
[0101] In general, the copolymer of 2-hydroxyethyl methacrylate and
acrylic and/or methacrylic acid, the copolymer of 2-hydroxyethyl
methacrylate, 4-hydroxybutyl acrylate and acrylic and/or
methacrylic acid, the copolymer of 2-hydroxyethyl methacrylate and
4-hydroxybutyl acrylate, and the homopolymer of 2-hydroxyethyl
methacrylate can be utilized in topical skin formulations,
including cosmetic compositions, dermatological preparations and
compositions, skin coatings or barriers. Some useful applications
of these polymers include use as sprayable carriers for topical
application of drugs to the skin. These polymers may also be a
component of a cream, including water in oil emulsions and oil in
water emulsions; lotions, which are suspensions in water or oil;
ointments, which are solutions in petroleum or polyethylene glycol;
or aerosols, which are sprayable solutions in water/alcohol and
gels.
[0102] The polymers may also be a component of a transdermal drug
delivery system. Specifically, the polymers can be used as a
carrier or vehicle to deliver an effective amount of a
pharmacologically active agent (drug) transdermally. In this
embodiment, the polymers may be loaded with an effective amount of
a pharmacologically active agent and locally placed on the surface
of the skin. The transdermal drug delivery system can also include,
as known in the art, skin permeation enhancers to facilitate the
transdermal delivery of the pharmacologically active agent. The
polymers can perform a dual function as a carrier of a
pharmacologically active agent and a protective coating or skin
barrier.
[0103] The polymers can also be sprayed onto the skin before the
application of adhesive-coated bandages, tapes, or other
adhesive-coated medical devices to prevent irritation of sensitive
skin.
[0104] The polymers can be used as an elastomeric medical film.
Preferably, the polymers can be coated onto a substrate, such as a
release liner and dried. The polymers will be self cross-linking
with heat treatment. Preferably, the polymers will be self
cross-linking by heat treating at a temperature in the range of
about 70.degree. C. to about 150.degree. C., more preferably in a
temperature range of about 70.degree. C. to about 125.degree. C.
The elastomeric medical film can be used directly over a wound on
the skin to provide a dressing or barrier. The elastomeric film is
soft and pliable, and easily conforms to the contours of human
skin.
[0105] The polymers may also be included in sun block and sunscreen
lotions, creams, sprays and as a carrier or vehicle of ultra-violet
(UV) light absorbers, such as aminobenzoic acid, benzophenone-8 and
benzophenone-4.
[0106] The polymers can be used as a carrier for cosmetic products.
Cosmetic compositions including the polymers are easy to apply to
and remove from the surface of human skin, are non-greasy, and
non-occlusive. Like skin, the polymers are hydrophilic, amphiphilic
and elastic.
[0107] The polymers can also be included as a component of a nasal
spray or other mucus membrane drug delivery systems, as a carrier
for a pharmacologically active agent, such as a pharmaceutical.
Using a mucus membrane drug delivery system is a potential benefit
over ingestion of pills, tablets or capsules, or repeated
injections of pharmacologically active agents, because these
traditional methods have initially high concentrations of the
pharmacologically active agent, which may be toxic or cause side
effects to the target organ or surrounding structures. As time
passes, the concentration of the pharmacologically active agent
diminishes and another dosage is required to maintain the
pharmacologically effective level. Utilizing a mucus membrane drug
delivery system including the polymers as a carrier for a
pharmacologically active agent may permit the delivery of an
effective amount of a pharmacologically active agent and
maintenance of the pharmacologically effective level over longer
periods of time.
[0108] The polymers can be blended with a polyalkylene glycol, such
as polyethylene glycol, to form a pressure sensitive adhesive. The
pressure sensitive adhesive can be coated onto a substrate, such as
a release liner, in the formation of a pressure sensitive product.
The pressure sensitive adhesive products can be used as a bandage,
tape, wound dressing, surgical drape, ostomy site dressing and the
like.
[0109] In another embodiment, the invention provides a method of
coating a substrate comprising applying to a substrate the
polymerization mixture any of the polymers that are prepared in a
solution of water and alcohol, and further comprising adding a
polyalkylene glycol to the polymerization mixture prior to the
removing of the alcohol and water, and thereafter forming a
hydrophilic pressure sensitive adhesive upon removing the alcohol
and water from the polymerization mixture. The polyalkylene glycol
to be added to the polymerization mixture includes, but is not
limited to, polyethylene glycol, polypropylene glycol, copolymers
of ethylene glycol and propylene glycol and mixtures thereof.
[0110] The polymers of the present invention may be applied to
various substrates as described below by any conventional means
known in the art such as die coating, roll coating, reverse roll
coating, gravure coating, reverse gravure coating, offset gravure
coating, Mayer rod or wire wound rod coating, spraying, brushing,
and the like. The polymers of the present invention may be heated
or cooled to facilitate the coating process to provide a desired
coating of the polymer on the substrate.
[0111] Any of the polymer products produced in accordance with the
present invention can be dried. The dried polymer may then be
pulverized into a powder, or sprayed dried into a powder.
[0112] The amount of the polymer that is to applied to a substrate
may be varied depending upon the characteristics of the substrate,
the characteristics desired to be imparted to the substrate, and
the particular characteristics of the polymers and copolymers. For
economic reasons, it is normally desired to apply the lowest amount
of coating to obtain the desired result. Typically, the applied
coating weights may, depending on the substrate and intended use,
range from about 0.1 to about 100 grams/meter.sup.2. For pressure
sensitive adhesive applications, the amount is preferably in the
range of about 15 grams/meter.sup.2 to about 45 grams/meter.sup.2.
For hydrophilic coating and ink jet coating applications, the
amount is preferably from about 1 gram/meter.sup.2 to about 25
grams/meter.sup.2.
[0113] The substrate which is used in the present invention may be
any substrate material such as paper, or polymeric films in the
form of sheets and strips, and the like. Preferred types of paper
include semi-gloss paper and high gloss paper. In one embodiment,
the substrate is a polymeric film. In a preferred embodiment, the
substrate is a polymeric film formed from a thermoplastic material.
In a more preferred embodiment, the substrate is a polymeric film
selected from the group consisting of polystyrene, a polyester, and
a polyolefin such as polyethylene or polypropylene.
[0114] Composites of the present invention may be prepared in
various forms including webs which may be in roll form and which
can thereafter be cut or slit into strips or sheets of desired
dimensions.
[0115] The polymers prepared in accordance with the methods of the
present invention are suitable for the preparation of and use as
elastomeric films, pressure sensitive adhesives, coatings,
precursors ro hydrogels, compositions for topical applications to
the skin such as, creams, lotions, ointments, gels, aerosols,
sprays, cosmetic compositions, dermatological preparations and
composotions, deodorants, and insect repellants.
[0116] As mentioned above, the unique combination of
characteristics makes the polymers suitable for use in medical
elastomeric films, bandages, tapes, wound care dressings, surgical
drapes, ostomy site dressings, as a carrier for transdermal drug
delivery systems, and as a carrier for mucus membrane drug delivery
systems. These medical products can be loaded with a
pharmacologically active agent. Typical pharmacologically active
agents include, but are not limited to, corticosteroids, anti-acne
agents such as retinoic acid and benzoyl peroxide, anti-infectives
such as erythromycin, tetracycline, and clindamycin, anti-fungals
such as tolnaftate, undecylenic acid, nystatin, clotrimazole, and
fluconazole, antioxidants such as butylated hydroxytoluene,
t-butylhydroquinone, tocopherol, surfactants such as sodium lauryl
sulfate, UV absorbers such as aminobenzoic acid, benzphenon-8, and
benzophenone-4, humectants such as propylene glycol, glycerin,
polyethylene glycol, and butylene glycol, alpha hydroxy acids, and
emollients such as castor oil, mineral oil, petroleum cetyl
palmitate, cetyl alcohol, and stearyl alcohol.
[0117] The following examples illustrate the methods of preparation
of the hydrophilic homopolymers and copolymers of the present
invention. It should be noted that the examples are intended for
illustrative purposes only, and are not intended to limit the scope
of the invention in any manner.
EXAMPLE 1
[0118] A copolymer of comprising 67.5 weight % 2-hydroxyethyl
methacrylate, 30 weight % 4-hydroxybutyl acrylate and 2.5 weight %
methacrylic acid was prepared according to the following recipe and
procedure:
1 Recipe Reactor Charge 2-Hydroxyethyl Methacrylate (Mitsubishi)
270 g 4-Hydroxybutyl acrylate 120 g Methacrylic acid 10 g Ethanol
373.2 g Deionized Water 373.2 g Initiator Charge Deionized Water 10
g Sodium Persulfate (0.5%) 2 g Cook-Off Initiator #1 Deionized
Water 5 g Ethanol 5 g Sodium Persulfate 0.4 g Cook off Initiator #2
Deionized Water 5 g Ethanol 5 g Sodium Persulfate 0.4 g Cook off
Initiator #3 Deionized Water 5 g Ethanol 5 g Sodium Metabisulfite
0.4 g Total 1189.6 g
Polymerization Procedure
[0119] 1. The Reactor Charge was weighed out into a flask and
introduced into a reaction kettle.
[0120] 2. The Reactor Charge was heated with a 80.degree. C. jacket
and with N.sub.2 purging of the Reactor Charge.
[0121] 3. The initiator charge was added to the heated and N.sub.2
purged Reactor Charge.
[0122] 4. After about 10 minutes, the polymerization was started
for a three hour period, while maintaining a jacket temperature of
about 83.degree. C.
[0123] 5. After about three hours of polymerization, Cook Off
Initiator #1 was added into the reaction kettle.
[0124] 6. One hour after adding Cook Off Initiator #1, Cook Off
Initiator #2 was added to the reaction kettle.
[0125] 7. One hour after adding Cook Off Initiator #2, Cook Off
Initiator #3 was added to the reaction kettle.
[0126] 8. After an additional hour of heating, the reaction kettle
was cooled.
[0127] The water insoluble copolymer prepared in Example 1 was
subjected to a leaching process to remove residual unreacted
monomer. The leaching process is described below.
Leaching Process
[0128] 1096 grams of polymer solution was transferred to the
leaching vessel and the leaching process to remove unreacted
monomer is described below.
2 First Leach Water added to precipitate polymer 2200 g Decant off
effluent 1708.8 g Ethanol to redissolve 160 g Second Leach Water
added to precipitate polymer 1100 g Decant off effluent 989.4 g
Ethanol to redissolve 120 g Third Leach Water added to precipitate
polymer 1100 g Decant off effluent 1366.5 g Ethanol to redissolve
140 g
[0129] After completion of the leaching process of the copolymer
product of Example 1, the pH of the leached copolymer was adjusted
with 4 grams of a 30% ammonium hydroxide solution. The copolymer
product was diluted to 5% total solids content (TSC) with water. By
visual inspection, the pH adjusted copolymer product appeared
slightly hazy in solution. The pH of the diluted copolymer was
further adjusted by the addition of 2 grams of 30% by weight
ammonium hydroxide solution. The copolymer product was again
diluted to 5% TSC with water. The pH of the copolymer product was
measured to be 6.6 and, upon visual inspection, the copolymer
product appeared clear in solution.
[0130] The leached and pH adjusted water soluble copolymer product
synthesized in Example No. 1, above, exhibited the following
properties:
3 Viscosity, cPs 864 % Solids content 20.9% % Ethanol 15.9% % Water
63.2% Residual monomer 2-Hydroxyethyl Methacrylate <15 ppm
4-Hydroxybutyl Acrylate <10 ppm Methacrylic Acid <0.01%
[0131] The presence of any gel formation in the copolymer product
was determined by visually inspecting the polymerization mixture or
a poured thin film of the copolymer product for any particulate.
The appearance of the copolymer product in this example was
determined utilizing a visual test looking at the clarity of a
poured thin film of the copolymer solution.
[0132] The percent solids in the copolymer product was measured by
accurately weighing a small aluminum dish, then accurately weighing
about 1 gram of wet copolymer sample. The aluminum dish with the
sample was dried under an infrared lamp for about 15 minutes. The
aluminum dish with the dried sample was cooled and then accurately
reweighed. The weight of the dried sample divided by the wet sample
multiplied by 100 is the percent total solids in the sample.
[0133] The viscosity of the copolymer product was measured under
ambient conditions (23-25.degree. C.) with a Brookfield LV
Viscometer using an appropriate spindle and speed for the measured
viscosity. The viscosity units are centipoise, cPs.
[0134] The protocols described hereinabove that were used to
measure and evaluate the appearance, percent solids and viscosity
of the copolymer product of Example No. 1 apply to all of the below
described inventive polymer examples produced according to the
present invention, and the comparative examples, unless
specifically indicated. The polymerization procedure described
above for Example 1, was used for Example Nos. 2-6, 10 and 11 and
Comparative Example Nos. 7-9, unless otherwise indicated.
EXAMPLE 2
[0135] A copolymer of comprising 97.5 weight % 2-hydroxyethyl
methacrylate and 2.5 weight % methacrylic acid was prepared
according to the following recipe:
4 Recipe Reactor Charge 2-Hydroxyethyl Methacrylate (Mitsubishi)
292.5 g Methacrylic acid 7.5 g Ethanol 280 g Deionized Water 280 g
Initiator Charge Deionized Water 10 g Sodium Persulfate (0.5%) 1.5
g Cook-Off Initiator #1 Deionized Water 5 g Ethanol 5 g Sodium
Persulfate 0.3 g Cook off Initiator #2 Deionized Water 5 g Ethanol
5 g Sodium Persulfate 0.3 g Cook off Initiator #3 Deionized Water 5
g Ethanol 5 g Sodium Metabisulfite 0.3 g Total 902.4 g
[0136] The water insoluble copolymer of Example 2 was subjected to
a leaching process to remove the residual unreacted monomer. The
leaching process is described below.
Leaching Process
[0137] 755 grams of polymer solution was transferred to the
leaching vessel and the polymer was subjected to the leaching
process to remove unreacted monomer, as described below.
5 First Leach Water added to precipitate polymer 1510 g Decant off
effluent 1207.7 g Ethanol to redissolve 120 g Second Leach Water
added to precipitate polymer 755 g Decant off effluent 986.2 g
Ethanol to redissolve 90 g Third Leach Water added to precipitate
polymer 755 g Decant off effluent 832.5 g Ethanol to redissolve 75
g
[0138] After completion of the leaching of the copolymer product of
Example 2, the leached copolymer was pH adjusted with 4 grams of a
30% ammonium hydroxide solution and 96 grams of deionized water.
The pH of the copolymer product was measured to be 6.4. The
copolymer was diluted to 5% total solids content with water and,
upon visual inspection, the copolymer product appeared clear in
solution.
[0139] The leached and pH adjusted copolymer product synthesized in
Example No. 2, above, exhibited the following properties:
6 Viscosity, cPs 12,140 % Solids content 23.7% % Ethanol 10.3% %
Water 66% Residual monomers 2-Hydroxyethyl Methacrylate <15 ppm
Methacrylic Acid <0.01%
EXAMPLE 3
[0140] A copolymer comprising 97.5 weight % 2-hydroxyethyl
methacrylate and 2.5 weight % methacrylic acid was prepared
according to the following recipe:
7 Reactor Charge 2-Hydroxyethyl Methacrylate (Mitsubishi) 292.5 g
Methacrylic acid 7.5 g Ethanol 280 g Deionized Water 280 g
Initiator Charge Deionized Water 10 g Sodium Persulfate (0.5%) 1.5
g Cook-Off Initiator #1 Deionized Water 5 g Ethanol 5 g Sodium
Persulfate 0.3 g Cook off Initiator #2 Deionized Water 5 g Ethanol
5 g Sodium Persulfate 0.3 g Cook off Initiator #3 Deionized Water 5
g Ethanol 5 g Sodium Metabisulfite 0.3 g Total 902.4 g
[0141] The water insoluble copolymer of Example 3 was subjected to
a leaching process to remove residual unreacted monomer. According
to this example, the copolymer product was redissolved in propylene
glycol instead of ethanol. The leaching process is described
below.
Leaching Process
[0142] 800 grams of polymer solution was transferred to the
leaching vessel and the polymer product was subjected to the
leaching process to remove unreacted monomer, as described
below.
8 First Leach Water added to precipitate polymer 1600 g Decant off
effluent 1397 g Propylene glycol to redissolve 165 g Second Leach
Water added to precipitate polymer 800 g Decant off effluent 1132 g
Propylene glycol to redissolve 140 g Third Leach Water added to
precipitate polymer 800 g Decant off effluent 996 g Propylene
glycol to redissolve 121 g
[0143] After completion of the leaching of the copolymer product of
Example 3, the leached copolymer was pH adjusted with 3 grams of a
30% ammonium hydroxide solution in 300 grams of deionized water.
The pH of the copolymer product was measured to be 5.8. The
copolymer was diluted to 5% total solids content with water and,
upon visual inspection, the copolymer product appeared clear in
solution. The leached and pH adjusted copolymer product synthesized
in Example No. 3, above, exhibited the following properties:
9 Viscosity, cPs 61,600 % Solids content 25.5% % Water 64.2% %
Propylene glycol 10.3% % Ethanol 0.7% Residual monomers
2-Hydroxyethyl Methacrylate <0.59% Methacrylic Acid
<0.01%
EXAMPLE 4
[0144] A copolymer of comprising 67.5 weight % 2-hydroxyethyl
methacrylate, 30 weight % 4-hydroxybutyl acrylate and 2.5 weight %
methacrylic acid was prepared according to the following
recipe:
10 Recipe Reactor Charge 2-Hydroxyethyl Methacrylate (Mitsubishi)
337.5 g 4-Hydroxybutyl acrylate 150 g Methacrylic acid 12.5 g
Ethanol 466.5 g Deionized Water 466.5 g Initiator Charge Deionized
Water 12.5 g Sodium Persulfate (0.5%) 2.5 g Cook-Off Initiator #1
Deionized Water 6.25 g Ethanol 6.25 g Sodium Persulfate 0.5 g Cook
off Initiator #2 Deionized Water 6.25 g Ethanol 6.25 g Sodium
Persulfate 0.5 g Cook off Initiator #3 Deionized Water 6.25 g
Ethanol 6.25 g Sodium Metabisulfite 0.5 g Total 1487 g
Leaching Process
[0145] 1000 grams of polymer solution was transferred to the
leaching vessel and the polymer product was subjected to a leaching
process to remove unreacted monomer, as described below.
11 First Leach Water added to precipitate polymer 2000 g Decant off
effluent 1225 g Ethanol to redissolve 145 g Second Leach Water
added to precipitate polymer 1000 g Decant off effluent 1189 g
Ethanol to redissolve 145 g Third Leach Water added to precipitate
polymer 1000 g Decant off effluent 1024 g Ethanol to redissolve 145
g Fourth Leach Water added to precipitate polymer 1000 g Decant off
effluent 1093 g
[0146] After completion of the leaching of the copolymer product of
Example 4, the copolymer product was both redissolved and the pH
adjusted in a solution of 4 grams of a 30% ammonium hydroxide
solution in 150 grams of deionized water. The copolymer product was
diluted to 5% total solids content (TSC) with water. Upon visual
inspection the copolymer product appeared slightly hazy. The pH of
the diluted copolymer was further adjusted by the addition of 2.4
grams of 30% by weight ammonium hydroxide solution. The copolymer
product was again diluted to 5% TSC with water. The pH was the
copolymer product was measured to be 7.6 and, upon visual
inspection, the copolymer product appeared clear in solution. The
leached and pH adjusted copolymer product synthesized in Example
No. 4, above, exhibited the following properties:
12 Viscosity, cPs 1904 % Solids content 18.4% % Ethanol 4% % Water
81.2% Residual monomers 2-Hydroxyethyl Methacrylate <15 ppm
4-Hydroxybutyl acrylate <20 ppm Methacrylic Acid <0.01%
EXAMPLE 5
[0147] 329 grams of polymer product prepared in accordance with
Example 4 was transferred to the leaching vessel and the polymer
product was subjected to a leaching process to remove unreacted
monomer, as described below.
13 LEACHING PROCESS First Leach Water added to precipitate polymer
660 g Decant off effluent 472.6 g Ethanol to redissolve 50 g Second
Leach Water added to precipitate polymer 330 g Decant off effluent
349.6 g Ethanol to redissolve 50 g Third Leach Water added to
precipitate polymer 330 g Decant off effluent 407.6 g
[0148] After completion of the leaching of the copolymer product,
the copolymer product was both redissolved and pH adjusted with a
solution containing 1.7 grams of triethanolamine in 50 grams of
deionized water and. Upon visual inspection, the copolymer product
appeared hazy in solution. The copolymer product was diluted to 5%
TSC with water. Upon visual inspection, the copolymer product
appeared milky in solution. The pH of the diluted copolymer product
was adjusted with an additional 2.1 grams of triethanolamine. The
pH of the copolymer was measured as 6.3. The copolymer product was
added diluted to 5% TSC and, upon visual inspection, the copolymer
was clear in solution. The leached and pH adjusted copolymer
product of Example No. 5 exhibited the following properties:
14 Viscosity, cPs 6480 % Solids content 20.3% % Ethanol 8.3% %
Water 71.4% Residual monomers 2-Hydroxyethyl Methacrylate <30
ppm 4-Hydroxybutyl acrylate <20 ppm methacrylic acid 0.1%
EXAMPLE 6
[0149] A copolymer comprising 60 weight % 2-hydroxyethyl
methacrylate, 30 weight % 4-hydroxybutyl acrylate and 10 weight %
methacrylic acid was prepared according to the following
recipe:
15 Recipe Reactor Charge 2-Hydroxyethyl Methacrylate (Mitsubishi)
240 g 4-Hydroxybutyl acrylate 120 g Methacrylic acid 40 g Ethanol
373.2 g Deionized Water 373.2 g Initiator Charge Deionized Water 10
g Sodium Persulfate (0.5%) 2 g Cook-Off Initiator #1 Deionized
Water 5 g Ethanol 5 g Sodium Persulfate 0.4 g Cook off Initiator #2
Deionized Water 5 g Ethanol 5 g Sodium Persulfate 0.4 g Cook off
Initiator #3 Deionized Water 5 g Ethanol 5 g Sodium Metabisulfite
0.4 g Total 1189.6 g
[0150] The water insoluble was subjected to a leaching process to
remove residual unreacted monomer. The leaching process is
described below.
Leaching Process
[0151] 1078 grams of copolymer solution of Example 6 was
transferred to the leaching vessel and copolymer was subjected to a
leaching process to remove unreacted monomer, as described
below.
16 First Leach Water to precipitate polymer 2000 g Decant off
effluent 1515.4 g Ethanol to redissolve 150 g Second Leach Water to
precipitate polymer 1000 g Decant off effluent 924.8 g Ethanol to
redissolve 150 g Third Leach Water to precipitate polymer 1000 g
Decant off effluent 1184.5 g Ethanol to redissolve 150 g
[0152] After completion of the leaching of the copolymer product of
Example 6, the pH of the leached copolymer was adjusted with 4
grams of a 30% ammonium hydroxide solution. Upon visual inspection,
the copolymer product appeared clear in solution. The copolymer
product was then diluted to 5% TSC with water. Upon visual
inspection, the copolymer product precipitated out of solution. The
pH of the diluted copolymer product was adjusted with 6 grams of a
30% ammonium hydroxide solution. The pH of the was measured as 6.5.
The copolymer product was again diluted to 5% TSC and, upon visual
inspection, the copolymer was clear in solution. The leached and pH
adjusted copolymer product synthesized in Example No. 6, above,
exhibited the following properties:
17 Viscosity, cPs 2920 % Solids content 19.9% % Ethanol 20.5% %
Water 59.6% Residual monomers 2-Hydroxyethyl Methacrylate <30
ppm 4-Hydroxybutyl acrylate <20 ppm Methacrylic Acid
<0.01%
Comparative Example 7
[0153] A copolymer of 67.5 weight % 2-hydroxyethyl methacrylate, 30
weight % 4-hydroxybutyl acrylate and 2.5 weight % methacrylic acid
was prepared according to the following recipe. The copolymer of
Comparative Example 7 was prepared with a
[0154] 2-hydroxyethyl methacrylate monomer source containing 0.17
weight % ethylene glycol dimethacrylate impurity, which monomer
source is commercially available from Rohm & Haas under the
tradename Rocryl 400:
18 Recipe Reactor Charge 2-Hydroxyethyl Methacrylate (Rohm &
Haas) 270 g 4-Hydroxybutyl acrylate 120 g Methacrylic acid 10 g
Ethanol 373.2 g Deionized Water 373.2 g Initiator Charge Deionized
Water 10 g Sodium Persulfate (0.5%) 2 g Cook-Off Initiator #1
Deionized Water 5 g Ethanol 5 g Sodium Persulfate 0.4 g Cook off
Initiator #2 Deionized Water 5 g Ethanol 5 g Sodium Persulfate 0.4
g Cook off Initiator #3 Deionized Water 5 g Ethanol 5 g Sodium
Metabisulfite 0.4 g Total 1139.6 g
[0155] The copolymer of Comparative Example 7 formed a hydrogel
during the polymerization process. Without being bound to any
particular theory, the inventor surmises that the formation of the
hydrogel can be attributed to the higher level of ethylene glycol
dimethacrylate present in the 2-hydroxyethyl methacrylate monomer
source from Rolun & Haas.
Comparative Example 8
[0156] A homopolymer of 2-hydroxyethyl methacrylate was prepared
according to the following recipe:
19 Recipe Reactor Charge 2-Hydroxyethyl Methacrylate (Mitsubishi)
233.4 g Ethanol 225.5 g Deionized Water 225.5 g Initiator Charge
Deionized Water 3.8 g Sodium Persulfate (0.5%) 1.17 g Cook-Off
Initiator #1 Deionized Water 1.9 g Ethanol 1.9 g Sodium Persulfate
0.23 g Cook off Initiator #2 Deionized Water 1.9 g Ethanol 1.9 g
Sodium Persulfate 0.23 g Cook off Initiator #3 Deionized Water 1.9
g Ethanol 1.9 g Sodium Metabisulfite 0.23 g Total 701.46 g
Leaching Process
[0157] 550 grams of the water insoluble copolymer prepared in
accordance with Comparative Example 8 was transferred to the
leaching vessel and the copolymer was subjected to a leaching
process to remove unreacted monomer, as described below.
20 First Leach Water added to precipitate polymer 1100 g Decant off
effluent 1361 g Ethanol to redissolve 100 g Second Leach Water
added to precipitate polymer 1000 g Decant off effluent 1105 g
Ethanol to redissolve 100 g Third Leach Water added to precipitate
polymer 1000 g Decant off effluent 1271 g Ethanol to redissolve 125
g
[0158] After completion of the leaching of the homopolymer of
Comparative Example 8, the pH of 90 grams of the leached
homopolymer was adjusted 9.7 with 0.28 grams of a 30% ammonium
hydroxide solution. The pH adjusted homopolymer product was diluted
to 5% TSC with water. Upon dilution, the homopolymer precipitated
out of solution, indicating that it was insoluble in water. The
leached and pH adjusted copolymer product synthesized in
Comparative Example No. 8 exhibited the following properties:
21 Viscosity, cPs 1900 % Solids content 25.6% % Ethanol 16.5% %
Water 57.9% Residual monomers 2-Hydroxyethyl Methacrylate <0.01%
4-Hydroxybutyl acrylate <0.01%
Comparative Example 9
[0159] A copolymer comprising 67 weight % 2-hydroxyethyl
methacrylate and 33 weight % 4-hydroxybutyl acrylate was prepared
in accordance with the following recipe:
22 Recipe Reactor Charge 2-Hydroxyethyl Methacrylate (Mitsubishi)
16.6 Kg 4-Hydroxybutyl acrylate 8.3 Kg Ethanol 24.1 Kg Deionized
Water 24.1 Kg Initiator Charge Deionized Water 0.4 Kg Sodium
Persulfate (0.5%) 0.13 Kg Cook-Off Initiator #1 Deionized Water 0.2
Kg Ethanol 0.2 Kg Sodium Persulfate 0.025 Kg Cook off Initiator #2
Deionized Water 0.2 Kg Ethanol 0.2 Kg Sodium Persulfate 0.025 Kg
Cook off Initiator #3 Deionized Water 0.2 Kg Ethanol 0.2 Kg Sodium
Persulfate (Metabisulfite) 0.025 Kg Total 75 Kg
Leaching Process
[0160] 75 kilograms of the water insoluble copolymer prepared in
accordance with Comparative Example 9 was transferred to the
leaching vessel and the copolymer was subjected to a leaching
process to remove unreacted monomer is described below.
23 First Leach Water to precipitate polymer 94.1 Kg Decant off
effluent 93.3 Kg Ethanol to redissolve 7.5 Kg Second Leach Water to
precipitate polymer 74.8 Kg Decant off effluent 92.9 Kg Ethanol to
redissolve 7.5 Kg Third Leach Water to precipitate polymer 74.8 Kg
Decant off effluent 81.5 Kg Ethanol to redissolve 9.4 Kg
[0161] After completion of the leaching of the copolymer product of
Comparative Example 9, the pH of 90 grams of the leached copolymer
adjusted with 0.022 grams of a 30% ammonium hydroxide solution. The
pH was measured to be about 8.38. Upon visual inspection, the
copolymer was clear in solution. The copolymer was then diluted to
5% TSC with water. Upon visual inspection, the diluted copolymer
product of Comparative Example 9 appeared as a milky dispersion in
solution. The leached and pH adjusted copolymer product synthesized
in Comparative Example No. 9, above, exhibited the following
properties:
24 Viscosity, cPs 660 % Solids content 23.6% % Ethanol 23.5% %
Water 52.9% Residual monomers 2-Hydroxyethyl Methacrylate <50
ppm 4-Hydroxybutyl acrylate <10 ppm
EXAMPLE 10
[0162] 1625 grams of the leached, water insoluble copolymer
prepared in accordance with Comparative Example 9 was transferred
to the leaching vessel and the copolymer was subjected to an
additional leaching process to replace the ethanol with propylene
glycol, as described below.
25 2.sup.nd LEACHING PROCESS First Leach Water to precipitate
polymer 1625 g Decant off effluent 1999 g Propylene glycol to
redissolve 150 g Second Leach Water to precipitate polymer 1625 g
Decant off effluent 2048 g Propylene glycol to redissolve 100 g
Third Leach Water to precipitate polymer 1625 g Decant off effluent
1788 g Propylene glycol to redissolve 100 g
[0163] The leached copolymer product of Example 10 exhibited the
following properties:
26 Viscosity, cPs 80,000 pH 3.2 % Solids content 29% % Water 59% %
Propylene glycol 12% % Ethanol 0.3% Residual monomers
2-Hydroxyethyl Methacrylate 90 ppm 4-Hydroxybutyl acrylate 25
ppm
EXAMPLE 11
[0164] A homopolymer of 2-hydroxyethyl methacrylate was prepared in
accordance with the following recipe:
27 Recipe Reactor Charge 2-Hydroxyethyl Methacrylate (Mitsubishi)
24.96 Kg Ethanol 24.12 Kg Deionized Water 24.12 Kg Initiator Charge
Deionized Water 0.41 Kg Sodium Persulfate (0.5%) 0.13 Kg Cook-Off
Initiator #1 Deionized Water 0.2 Kg Ethanol 0.2 Kg Sodium
Persulfate 0.025 Kg Cook off Initiator #2 Deionized Water 0.2 Kg
Ethanol 0.2 Kg Sodium Persulfate 0.025 Kg Cook off Initiator #3
Deionized Water 0.2 Kg Ethanol 0.2 Kg Sodium Metabisulfite 0.025 Kg
Total 74.59 Kg % Solids Content 34.7%
[0165] The was subjected to a leaching process to remove the
residual unreacted 2-hydroxyethyl methacrylate monomer.
Leaching Process
[0166] 75 kilograms of the water insoluble homopolymer prepared in
accordance with Example 11 was transferred to the leaching vessel
and the polymer was subject to a leaching process to remove
unreacted monomer, as described below.
28 First Leach Water to precipitate polymer 131.6 Kg Decant off
effluent 105.3 Kg Ethanol to redissolve 8.5 Kg Second Leach Water
to precipitate polymer 73.5 Kg Decant off effluent 84.4 Kg Ethanol
to redissolve 7.8 Kg Third Leach Water to precipitate polymer 74.9
Kg Decant off effluent 84.1 Kg Ethanol to redissolve 9.4 Kg
2.sup.nd Leaching Process
[0167] 1624 grams of leached polymer prepared in accordance with
Example 11 was transferred to the leaching vessel and the polymer
was subjected to a further leaching process to replace the ethanol
with propylene glycol, as described below.
29 First Leach Water to precipitate polymer 1624 g Decant off
effluent 2062 g Propylene glycol to redissolve 154 g Second Leach
Water to precipitate polymer 1624 g Decant off effluent 1873 g
Propylene glycol to redissolve 108 g Third Leach Water to
precipitate polymer 1624 g Decant off effluent 1718 g Propylene
glycol to redissolve 103 g
[0168] The leached copolymer product synthesized in Example 11,
above, exhibited the following properties:
30 Viscosity, cPs 540,000 pH 3.5 % Solids content 28% % Water 58% %
Propylene glycol 14% % Ethanol 0.5% Residual monomer 2-Hydroxyethyl
Methacrylate <10 ppm
[0169] While the invention has been explained in relation to its
preferred embodiments, it is to be understood that various
modifications thereof will become apparent to those skilled in the
art upon reading the specification. Therefore, it is to be
understood that the invention disclosed herein is intended to cover
such modifications as fall within the scope of the appended
claims.
* * * * *